WO2022198873A1 - Octanol production system and method - Google Patents

Abstract

An octanol production system, comprising: a carbonyl reactor (10) and a butyraldehyde separation device (30); the carbonyl reactor (10) is connected to the butyraldehyde separation device (30); an n-butyraldehyde outlet (302) is provided on the butyraldehyde separation device (30); a condensation reactor (80) is connected to the n-butyraldehyde outlet (302); a first reboiler (40) and a first pre-disperser (50) are provided between the condensation reactor (80) and the butyraldehyde separation device (30); both the gas phase outlet and the liquid phase outlet of the first reboiler (40) are connected to the first pre-disperser (50); n-butyraldehyde separated by the butyraldehyde separation device (30) flows out from the n-butyraldehyde outlet (302), and is dispersed into n-butyraldehyde bubbles through the first reboiler (40) and the first pre-disperser (50) and then the n-butyraldehyde bubbles are introduced into the condensation reactor (80); a micro-interface generator (801) is provided in the condensation reactor (80); the micro-interface generator (801) is connected to the first pre-disperser (50) to further disperse the n-butyraldehyde bubbles into micron-sized micro-bubbles.

Description

A kind of production system and method of octanol technical field

The invention relates to the field of propylene hydroxylation reaction preparation, in particular to a system and method for producing octanol.

Background technique

Octanol is an important raw material for the synthesis of fine chemical products. At present, the output of octanol in my country is huge, accounting for about 21% of the world's total. Octanol uses synthesis gas and propylene as raw materials, and generates n-isobutyraldehyde through formylation reaction, and then obtains n-isobutanol can also be condensed with two molecules of n-butyraldehyde to form unsaturated bonds to obtain octanol. Octanol has the typical characteristics of alcoholic organics, and all have special odor. It is a colorless, transparent, flammable liquid with moderate toxicity and can form an azeotrope with water. Mainly used in the production of plasticizers, solvents, dehydrating agents, defoaming agents, dispersants, flotation agents, petroleum additives and synthetic fragrances. Due to its wide range of uses, the production and dosage of octanol are also increasing year by year.

The main production methods of octanol include fermentation method, acetaldehyde condensation method and propylene oxo method. Among them, propylene oxo method has developed rapidly with remarkable advantages in the world and is the main method for producing butanol and octanol.

The steps of preparing octanol by propylene oxo method are as follows:

(1) generation of butyraldehyde: take synthesis gas and propylene as raw materials, take carbonyl rhodium, triphenylphosphine complex or other industrially used similar substances as catalysts, react to produce mixed butyraldehyde, separate the catalyst and further Rectifying and separating to obtain butyraldehyde mixture;

(2) the generation of butanol: the butyraldehyde mixture enters the butyraldehyde hydrogenation system to generate butanol, and then removes light heavy components through rectification, and separates isomers to obtain n-butanol and isobutanol;

(3) Generation of octanol: n-butyraldehyde enters the condensation system for carbonyl condensation to produce octenal, and then hydrogenation and rectification are added to remove light and heavy components to finally produce octanol.

The main equation for the preparation of octanol by propylene oxo is as follows:

(1) Propylene hydroformylation generates n-butyraldehyde (n-Bal):

CH3CH _{= CH2 +} CO+ _{H2 → CH3CH2CH2CHO}

(2) Propylene hydroformylation generates isobutyraldehyde (i-Bal):

CH ₃ CH=CH ₂ +CO+H ₂ →CH ₃ CH ₂ (CHO)CH ₃

(3) hydrogenation of mixed butyraldehyde generates isobutanol and n-butanol:

_{CH3CH2CH2CHO + H2 → CH3CH2CH2CH2OH _ _ _}

CH3CH2(CHO) _{CH3 + H2 → CH3CH} ( _{CH3 )} CH2OH

(4) n-butyraldehyde condensation reaction generates 2-ethyl-3-propyl acrolein (EPA):

2CH ₃ CH ₂ CH ₃ CHO→CH ₃ CH ₂ CH ₂ CH=C(C ₂ H ₅ )CHO+H ₂ O

(5) Hydrogenation of 2-ethyl-3-propyl acrolein to generate octanol:

_{CH3CH2CH2CH =} C( _{C2H5 )} CHO _{+ 2H2 → CH3CH2CH2CH ( CH2CH3 ) CH2OH}

Chinese Patent Publication No.: CN103012089A discloses a method for oxo synthesis of propylene, comprising sending propylene, stripped synthesis gas and hydroformylation catalyst solution into a first oxo butyraldehyde condensation unit for contact reaction, and the butyraldehyde condensation unit The foam component containing the hydroformylation catalyst is sent to the first separator for separation, a part of the obtained gas phase component is returned, and the other part is sent to the second oxo butyraldehyde for condensation with the synthesis gas and the hydroformylation catalyst solution. Contact reaction in the unit, and the foam component containing the hydroformylation catalyst in the butyraldehyde condensation unit is sent to the second separator for separation; at least part of the first and second oxo-butyraldehyde condensation unit bottoms are The liquid phase and the synthesis gas are sent together into the stripping tower for stripping, the liquid phase components are obtained at the bottom of the tower, and the stripped synthesis gas is obtained at the top of the tower; the liquid phase components at the bottom of the stripping tower are sent to the separation tower for separation, The crude butyraldehyde product is extracted from the top of the tower, and the catalyst solution is extracted from the bottom of the tower. The method can effectively improve the utilization rate of propylene and reduce the content of propylene in the tail gas. It can be seen that the method has the following problems:

First, in the method, propylene, synthesis gas and the catalyst are only contacted by the first oxo butyraldehyde condensation unit, and the gas phase components enter the first oxo to form large bubbles. However, because the bubble volume is too large, it cannot be combined with the liquid phase. The sub-catalysts are fully contacted, which reduces the reaction efficiency of the system.

Second, in the method, the reaction rate of the synthesis gas, propylene and the catalyst is reduced, resulting in a reduction in the utilization rate of propylene and synthesis gas, causing waste of raw materials to a large extent, and increasing the production cost of octanol, which is not in line with the existing circular economy. requirements.

Thirdly, the method does not take into account the problems of small phase boundary area, serious droplet condensation and low reaction efficiency in the direct reaction between lye and n-butyraldehyde solution.

Fourth, the hydrogenation reaction in the method utilizes a fixed-bed reactor. Since it 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 this, the present invention is proposed.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a system for producing octanol, which pre-disperses n-butyraldehyde into macro-bubbles by using a first pre-disperser, and then disperses and breaks it into micro-bubbles through a micro-interface generator, The mass transfer area of the phase boundary between n-butyraldehyde and lye is increased, which is beneficial to improve the reaction efficiency; by setting the first pre-disperser, it is beneficial to improve the generation rate of micro-bubbles; The air bubbles are evenly distributed.

The second object of the present invention is to provide a reaction method for producing octanol using the above-mentioned production system. The reaction method is easy to operate, has high butyraldehyde conversion rate and high product quality, is beneficial to reduce energy consumption, and achieves higher efficiency than existing processes. good response.

In order to realize the above-mentioned purpose of the present invention, the following technical solutions are specially adopted:

The invention provides an octanol production system, comprising: a carbonyl reactor and a butyraldehyde separation device; the carbonyl reactor is connected with the butyraldehyde separation device; the butyraldehyde separation device is provided with an n-butyraldehyde outlet , the n-butyraldehyde outlet is connected with a condensation reactor, a first reboiler and a first pre-disperser are arranged between the condensation reactor and the butyraldehyde separation device, and the gas phase outlet of the first reboiler and the liquid phase outlet are both passed into the first predispersor; the n-butyraldehyde separated by the butyraldehyde separation device flows out from the n-butyraldehyde outlet, and passes through the first reboiler and the first reboiler. A pre-disperser is dispersed into n-butyraldehyde bubbles and passed into the condensation reactor;

A micro-interface generator is arranged in the condensation reactor, and the micro-interface generator is connected with the first pre-disperser to further disperse the n-butyraldehyde bubbles into micro-level micro-bubbles; the condensation reactor A rotating shaft is arranged longitudinally inside, and the rotating shaft penetrates the bottom of the condensation reactor and is connected with a motor; the part of the rotating shaft located in the condensation reactor is provided with a plurality of stirring paddles; the top of the rotating shaft is connected with distribution disk; the distribution disk is arranged at the outlet of the micro-interface generator;

The distribution disk is conical; a plurality of guide holes are evenly distributed on the distribution disk to evenly distribute the micro-bubbles generated by the micro-interface generator;

The material outlet of the condensation reactor is connected with a hydrogenation reactor, a second reboiler and an external microbubble generator are arranged between the hydrogenation reactor and the condensation reactor, and the condensation reactor generates The octenal is divided into a gas-phase stream and a liquid-phase stream through the second reboiler, and the gas-phase stream and the liquid-phase stream are all passed into the external micro-bubble generator, and in the external-type micro-bubble generator. After being dispersed into micron-sized octenal microbubbles, flow into the hydrogenation reactor;

The hydrogenation reactor is provided with a built-in micro-bubble generator, and the built-in micro-interface generator is connected with the hydrogen cylinder; a second pre-disperser is arranged between the hydrogen cylinder and the built-in micro-interface generator , the second pre-disperser is located outside the hydrogenation reactor; after the hydrogen is dispersed into hydrogen bubbles by the second pre-dispersor, it is again dispersed into micron-scale hydrogen micro-bubbles inside the built-in micro-interface generator.

In the prior art, in the direct reaction between the lye and the n-butyraldehyde solution, the phase boundary area is small, the droplet condensation phenomenon is serious, and the reaction efficiency is low. In addition, in the subsequent hydrogenation reaction of octenal generated, there are also problems of small contact area and low reaction efficiency, which seriously affect the yield of the generated octanol.

In order to solve the above-mentioned technical problems, the present invention provides a system for producing octanol, which uses a first pre-disperser to pre-disperse n-butyraldehyde into large bubbles and then disperses and breaks it by a micro-interface generator. The formation of microbubbles increases the mass transfer area of the phase boundary between n-butyraldehyde and lye, which is beneficial to improve the reaction efficiency; the use of the first pre-disperser is beneficial to increase the generation rate of microbubbles. The outlet of the micro-interface generator of the present invention is also provided with a distribution disc, which can promote the redistribution of micro-bubbles in the condensation reactor; in addition, the distribution disc of the present invention is connected with a rotating shaft, and the rotating shaft drives the distribution The disc rotates, which can further promote the uniform distribution of the micro-bubbles; the stirring paddle set on the rotating shaft is also to promote the uniform distribution of the micro-bubbles, thereby improving the reaction efficiency.

It can be seen that the present invention improves the application effect of the micro-interface generator by combining the first pre-disperser, the micro-interface generator, the distribution disc and the stirring paddle.

In addition, in the present invention, a built-in micro-bubble generator is arranged in the hydrogenation reactor to disperse and break the hydrogen gas into micro-bubbles, and the external micro-bubble generator disperses and breaks octenal into micro-bubbles, thereby improving octenal and octenal. The phase boundary contact area of hydrogen increases the conversion rate and reaction rate.

Preferably, both the first pre-dispersor and the second pre-dispersor are provided with multiple layers of dispersion layers, and the dispersion layers are formed by stacking a plurality of circular granules with different diameters. The granular material can be made of acid-resistant and corrosion-resistant materials. The circular granular bodies between the two adjacent layers cooperate with each other to form multiple gaps of the same size. The gas passes through the gaps to form bubbles, which improves the mass transfer on the gas surface. area.

Preferably, the side wall of the condensation reactor is provided with a liquid injector for injecting alkali liquid, the liquid injector comprises a semicircular injector main body and a spray head uniformly arranged on the semicircular surface of the injector main body ; the liquid injector is located below the micro-interface generator along the vertical direction; the liquid injector is connected with an alkali liquid storage tank. By spraying the lye solution through a liquid injector, the contact area with n-butyraldehyde can be increased, and the conversion rate of n-butyraldehyde can be improved.

Preferably, two bubble distributors with opposite outlets are arranged inside the hydrogenation reactor, the bubble distributor located above is connected to the built-in micro-bubble generator, and the bubble distributor located below is connected to the built-in micro-bubble generator. An external microbubble generator is connected. The bubble distributor can make the bubbles evenly distributed, and the outlet can relatively make the octenal bubbles and the hydrogen bubbles hedged, which further promotes the even distribution of the bubbles.

Preferably, the bubble distributor includes a distributor body and a plurality of nozzles; the plurality of nozzles are obliquely arranged on the distributor body to uniformly disperse the micro-bubbles. The nozzle can redistribute the micro-bubbles, preventing a large number of micro-bubbles from gathering together, and the micro-bubbles enter the main body of the distributor and are sprayed in different directions through the nozzle.

Preferably, a solvent inlet is arranged at the bottom of the carbonyl reactor; a propylene inlet and a synthesis gas inlet are arranged on the side wall of the carbonyl reactor in sequence; two micro-interfaces with opposite outlets are arranged in the carbonyl reactor to generate The micro-interface generator located above is connected to the propylene inlet, and the micro-interface generator located below is connected to the synthesis gas inlet. A bubble distributor is arranged at the outlet of the two micro-interface generators.

Preferably, a catalyst injector is further arranged on the side wall of the carbonyl reactor, and the catalyst injector is arranged vertically between the two micro-interface generators. The catalyst injector has the same structure as the liquid injector.

The carbonyl reactor of the invention is provided with two micro-interface generators to disperse and crush propylene and synthesis gas respectively. During the reaction, propylene and synthesis gas are dispersed and crushed into micro-level micro-bubbles by the micro-interface generator respectively, and then carbonylation is carried out. The reaction increases the mass transfer area of the phase boundary between propylene and synthesis gas; the outlets of the two micro-interface generators are opposed to each other, which can play a hedging effect to achieve uniform distribution of micro-bubbles.

It should be noted that, when the micro-interface generators are arranged in the present invention, the micro-interface generator located in the upper part is connected with the propylene inlet, and the micro-interface generator located in the lower part is connected with the synthesis gas inlet, and the synthesis gas is relatively the gas source. It needs to be synthesized in advance, and the raw materials are all flammable and explosive gases, so in order to improve its safety, try to set the position of its air inlet as low as possible. Therefore, the micro-interface generator for crushing propylene is set in the upper part, and the micro-interface generator for crushing syngas is set in the lower part. This arrangement also fully considers safety, reaction efficiency and other factors. After the micro-interface generator is sufficiently broken and dispersed, it will pass through the gas distributor located on the upper part of the micro-interface generator with a higher probability to achieve a more uniform distribution.

In order to improve the reaction efficiency of n-butyraldehyde and lye, the present invention uses a first pre-disperser to pre-disperse n-butyraldehyde into large bubbles, and then disperses and breaks it into micro-bubbles through a micro-interface generator, thereby improving the efficiency of n-butyraldehyde and lye. The phase boundary mass transfer area of the lye; the use of the first pre-disperser is beneficial to improve the generation rate of microbubbles.

The outlet of the micro-interface generator of the present invention is also provided with a distribution disc, which can promote the redistribution of micro-bubbles in the condensation reactor; in addition, the distribution disc of the present invention is connected with a rotating shaft, and the rotating shaft drives the distribution The disc rotates, which can further promote the uniform distribution of the micro-bubbles; the stirring paddle set on the rotating shaft is also to promote the uniform distribution of the micro-bubbles, thereby improving the reaction efficiency. It can be seen that the present invention improves the application effect of the micro-interface generator by combining the first pre-disperser, the micro-interface generator and the distribution disc.

In addition, in the present invention, a built-in micro-bubble generator is arranged in the hydrogenation reactor to disperse and break the hydrogen gas into micro-bubbles, and the external micro-bubble generator disperses and breaks octenal into micro-bubbles, thereby improving octenal and octenal. The phase boundary contact area of hydrogen improves the conversion rate and reaction rate, and at the same time, by combining the second pre-disperser with the built-in microbubble generator, the generation efficiency of hydrogen microbubbles is improved.

Those skilled in the art can understand that the micro-interface generator used in the present invention has been embodied in the inventor's prior patents, such as application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U. In the previous patent CN201610641119.6, the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator) were introduced in detail. There is a cavity, the body is provided with an inlet communicating with the cavity, the opposite first and second ends of the cavity are open, wherein the cross-sectional area of the cavity is from the middle of the cavity to the first and second ends of the cavity. The second end is reduced; the secondary crushing piece is arranged at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is arranged in the cavity, and both ends of the secondary crushing piece and the cavity are open An annular channel is formed between the through holes of the micro-bubble generator. The micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe." From the specific structure disclosed in the application document, we can know that its specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe. In the bubble generator, ultra-high-speed rotation and cutting of the gas make the gas bubbles break into micro-bubbles at the micron level, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micro-bubble generator in this patent belongs to the pneumatic micro-interface generation. device.

In addition, the previous patent 201610641251.7 records that the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed port with the gas-liquid mixture outlet, indicating that the bubble breaker is both It needs to be mixed with gas and liquid. In addition, it can be seen from the following drawings that the primary bubble breaker mainly uses circulating liquid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is a gas-liquid breaker. The mixture is simultaneously fed into the elliptical rotating ball for rotation, so that the bubbles are broken during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage type micro-interface generator. In fact, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, they all belong to a specific form of the micro-interface generator. However, the micro-interface generator used in the present invention is not limited to the above several forms. , 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 take. In addition, the previous patent 201710766435.0 recorded that "the principle of the bubble breaker is to achieve high-speed jets to achieve gas collision", and also stated that it can be used in micro-interface enhanced reactors to verify the relationship between the bubble breaker and the micro-interface generator. and the prior patent CN106187660 also has related records for the specific structure of the bubble breaker, see the specific description in paragraphs [0031]-[0041], and the accompanying drawings, which are related to the bubble breaker S-2 The specific working principle of the bubble breaker is explained in detail. The top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet. The liquid phase entering from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the accompanying drawings. The bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.

Since the micro-interface generator was just developed in the early stage of the previous patent application, it was named as micro-bubble generator (CN201610641119.6), bubble breaker (201710766435.0), etc., and later changed its name to micro-interface generator with continuous technological improvement. The micro-interface generator and micro-interface generator in the present invention are equivalent to the previous micro-bubble generator, bubble breaker, etc., but the names are different. To sum up, the micro-interface generator of the present invention belongs to the prior art.

Preferably, a rectification column is connected to the material outlet of the hydrogenation reactor; the octanol produced by the hydrogenation reactor is rectified and discharged by the rectification column.

Preferably, the hydrogenation reactor is a slurry bed reactor.

Preferably, the carbonyl reactor is connected with a catalyst circulation device for supplementing the catalyst.

Preferably, a demister is arranged between the carbonyl reactor and the butyraldehyde separation device, and the product of the carbonyl reactor flows into the butyraldehyde separation device after being defoamed by the demister.

The present invention also provides a reaction method using the above-mentioned production system, comprising the steps of:

Mix propylene and synthesis gas with catalyst, carry out hydroxyl synthesis reaction, and then obtain crude product after defoaming, and the crude product is separated to obtain n-butyraldehyde;

After the n-butyraldehyde is broken by the micro-interface, it is subjected to a condensation reaction with the lye to generate octenal, and the octenal and hydrogen are respectively subjected to micro-interface fragmentation, and the crude octanol product is obtained after the hydrogenation reaction, and the crude octanol product is obtained. The product octanol is obtained after rectification and purification.

Preferably, the reaction temperature for the synthesis of the hydroxyl group is 80-95° C., and the pressure is 0.8-1.3 MPa; the catalyst is a rhodium catalyst.

Preferably, the reaction temperature in the condensation reactor is 65-75° C., and the reaction pressure is 0.23-0.28 MPa.

Further, the reaction temperature in the hydrogenation reactor is 60-78° C., and the reaction pressure is 0.50-0.80 MPa.

Further, the hydrogenation reaction catalyst is a metal such as nickel, chromium, and an oxide catalyst triphenylphosphine solution or other industry-approved auxiliaries of the same type to participate in the reaction.

The octanol product obtained by the reaction method of the invention has good quality, high yield and high conversion rate of butyraldehyde. In addition, the preparation method itself has low reaction temperature, greatly reduced pressure and significantly reduced cost.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The generation system of the present invention improves the phase boundary between n-butyraldehyde and lye by pre-dispersing n-butyraldehyde into large bubbles by using a first pre-disperser and then dispersing and breaking it into micro-bubbles through a micro-interface generator The mass transfer area is beneficial to improve the reaction efficiency;

(2) By setting the first pre-dispersor, it is beneficial to improve the generation rate of microbubbles;

(3) By arranging a distribution disk at the outlet of the micro-interface generator, the uniform distribution of the generated micro-bubbles can be promoted.

Description of 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 for the purpose of illustrating preferred embodiments only and are not to be considered limiting of the invention. Also, the same components are denoted by the same reference numerals throughout the drawings. In the attached image:

Fig. 1 is the structural representation of the production system of octanol provided by the embodiment of the present invention 1;

[Correction 17.08.2021 in accordance with Rule 91]
Fig. 2 is the structural representation inside the condensation reactor provided by the embodiment of the present invention 1;

3 is a schematic structural diagram of a bubble distributor provided in Embodiment 1 of the present invention;

4 is a schematic structural diagram of a first predisperser provided in Embodiment 1 of the present invention;

FIG. 5 is a schematic structural diagram of the catalyst injector provided in Example 1 of the present invention.

Description of drawings:

10-carbonyl reactor; 101-propylene import;

102-Syngas inlet; 103-Solvent inlet;

104-catalyst injector; 1041-injector body;

1042-jet head; 105-micro interface generator;

106-bubble distributor; 1061-distributor main body;

1062-nozzle; 20-demister;

30-butyraldehyde separation device; 301-mixed butyraldehyde outlet;

302-n-butyraldehyde export; 40-first reboiler;

50-first pre-disperser; 501-dispersion layer;

60-Hydrogen cylinder; 70-Second pre-disperser;

80-condensation reactor; 801-micro interface generator;

802-liquid ejector; 803-rotating shaft;

804-stirring paddle; 805-distribution disc;

90-lye storage tank; 100-second reboiler;

110-external micro-bubble generator; 120-hydrogenation reactor;

1201-built-in micro-bubble generator; 130-rectification tower;

140-motor; 150-catalyst circulation device.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments, but those skilled in the art will understand that the embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments, It is only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. The indicated orientation or positional relationship is based on the orientation or positional relationship shown in the accompanying drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the indicated device or element must have a specific orientation or a specific orientation. construction and operation, and therefore should not be construed as limiting the invention. Furthermore, the terms "first", "second", and "third" are used for descriptive purposes only and should not be construed to indicate or imply relative importance.

In the description of the present invention, it should be noted that the terms "installed", "connected" and "connected" should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood in specific situations.

In order to illustrate the technical solutions of the present invention more clearly, the following descriptions are given in the form of specific embodiments.

Example 1

As shown in Figures 1-5, this embodiment provides an octanol production system, including: a carbonyl reactor 10 and a butyraldehyde separation device 30; the carbonyl reactor 10 is connected to the butyraldehyde separation device 30; the carbonyl reactor 10 A demister 20 is arranged between the device and the butyraldehyde separation device 30 , and the product of the carbonyl reactor 10 flows into the butyraldehyde separation device 30 after being defoamed by the demister 20 .

Wherein, the bottom of the carbonyl reactor 10 is provided with a solvent inlet 103; the side wall of the carbonyl reactor 10 is provided with a propylene inlet 101 and a synthesis gas inlet 102 in sequence; two micro-interface generators with opposite outlets are arranged in the carbonyl reactor 10 105 , the upper micro-interface generator 105 is connected to the propylene inlet 101 , and the lower micro-interface generator 105 is connected to the syngas inlet 102 . A bubble distributor 106 is provided at the outlet of the two micro-interface generators 105 .

A catalyst injector 104 is also arranged on the side wall of the carbonyl reactor 10 , and the catalyst injector 104 is arranged between the two micro-interface generators 105 in the vertical direction.

In this embodiment, the butyraldehyde separation device 30 is provided with an n-butyraldehyde outlet 302 and a mixed butyraldehyde outlet 301, and the n-butyraldehyde outlet 302 is connected with a condensation reactor 80, and a condensation reactor 80 is provided between the butyraldehyde separation device 30 There are a first reboiler 40 and a first predispersor 50, and the gas phase outlet and the liquid phase outlet of the first reboiler 40 are both passed into the first predisperser 50; the n-butyraldehyde separated by the butyraldehyde separation device 30 It flows out from the n-butyraldehyde outlet 302, is dispersed into n-butyraldehyde bubbles through the first reboiler 40 and the first pre-dispersor 50, and then passes into the condensation reactor 80.

As shown in FIG. 2, a micro-interface generator 801 is arranged in the condensation reactor 80, and the micro-interface generator 801 is connected with the first pre-disperser 50 to further disperse the n-butyraldehyde bubbles into micro-bubbles of micron level; the condensation reactor A rotating shaft 803 is longitudinally arranged inside the 80, and the rotating shaft 803 penetrates the bottom of the condensation reactor 80 and is connected with a motor 140; the part of the rotating shaft 803 located in the condensation reactor 80 is provided with a plurality of stirring paddles 804; The disc 805; the distribution disc 805 is arranged at the outlet of the micro-interface generator 801;

Wherein, the distribution disk 805 is tapered; the distribution disk 805 is evenly distributed with a plurality of guide holes to evenly distribute the micro-bubbles generated by the micro-interface generator 801;

As shown in FIG. 3 , the side wall of the condensation reactor 80 is provided with a liquid injector 802 for injecting alkali liquid. The liquid injector 802 includes a semicircular injector body 1041 and a The spray head 1042; the liquid sprayer 802 is located below the micro-interface generator 801 in the vertical direction; the liquid sprayer 802 is connected with the lye storage tank 90. By spraying the lye solution through the liquid injector 802, the contact area with n-butyraldehyde can be increased, and thus the conversion rate of n-butyraldehyde can be increased.

In this embodiment, the catalyst injector 104 has the same structure as the liquid injector 802 .

A hydrogenation reactor 120 is connected to the material outlet of the condensation reactor 80, and a second reboiler 100 and an external microbubble generator 110 are arranged between the hydrogenation reactor 120 and the condensation reactor 80. Octenal is divided into gas-phase stream and liquid-phase stream through the second reboiler 100, and both the gas-phase stream and the liquid-phase stream are passed into the external micro-bubble generator 110, and are dispersed into micron-level in the external micro-bubble generator 110. The octenal microbubbles then flow into the hydrogenation reactor 120 .

The hydrogenation reactor 120 is provided with a built-in micro-bubble generator 1201, and the built-in micro-interface generator 801 is connected to the hydrogen cylinder 60; a second pre-disperser 70 is arranged between the hydrogen cylinder 60 and the built-in micro-interface generator 801, and the second The pre-disperser 70 is located outside the hydrogenation reactor 120 ; the hydrogen is dispersed into hydrogen bubbles by the second pre-dispersor 70 and then dispersed into micron-scale hydrogen micro-bubbles inside the built-in micro-interface generator 801 . The octenal microbubbles react with the hydrogen microbubbles, and the reaction product enters the rectifying tower 130 for rectification.

As shown in FIG. 4 , both the first pre-dispersor 50 and the second pre-dispersor 70 are provided with a multi-layer dispersion layer 501 , and the dispersion layer 501 is formed by stacking a plurality of circular granular bodies with different diameters. The granular material can be made of acid-resistant and corrosion-resistant materials. The circular granular bodies between two adjacent layers cooperate with each other to form a plurality of gaps of the same size, and the gas passes through the gaps to form bubbles.

In this embodiment, the hydrogenation reactor 120 is provided with two bubble distributors 106 with opposite outlets. The bubble distributor 106 located above is connected to the built-in micro-bubble generator 1201, and the bubble distributor 106 located below is connected to the external micro-bubble generator 1201. A bubble generator 110 is connected. The bubble distributor 106 can make the bubbles evenly distributed, and the outlet can relatively create a hedge between the octenal bubbles and the hydrogen bubbles, which further promotes the even distribution of the bubbles.

The bubble distributor 106 includes a distributor main body 1061 and a plurality of nozzles 1062; the plurality of nozzles 1062 are obliquely arranged on the distributor main body 1061 to uniformly disperse the micro-bubbles. The nozzle 1062 can redistribute the micro-bubbles, preventing a large number of micro-bubbles from gathering together, and the micro-bubbles enter the distributor body 1061 and are sprayed in different directions through the nozzle 1062.

Wherein, the hydrogenation reactor 120 is a slurry bed reactor.

In order to reduce the waste of catalyst, the carbonyl reactor 10 is connected with a catalyst circulation device 150 for supplementing the catalyst. The catalyst circulation device 150 can also promote the recycling of the catalyst and save the cost.

In this embodiment, the solvent in the carbonyl reactor 10 is n-butyraldehyde, the solvent in the hydrogenation reactor 120 is octanol, and the solvent in the condensation reactor 80 is octanol.

During the specific operation, the propylene gas and the synthesis gas are passed into the carbonyl reactor 10, the reaction temperature in the carbonyl reactor 10 is set to 80° C., the reaction pressure is set to 0.8MPa, and the micro-interface generator 105 breaks the propylene and the synthesis gas into pieces. The micro-bubbles are formed into micro-sized bubbles, and the micro-bubbles are released into the carbonyl reactor 10, so that the materials are fully contacted and the oxo reaction is carried out.

The oxo reaction product is transported to the butyraldehyde separation device 30, and the n-butyraldehyde enters the micro-interface generator 801 through the first pre-disperser 50, and the micro-interface generator 801 smashes the n-butyraldehyde into micron-scale micro-bubbles, and It is released into the condensation reactor 80, so that the n-butyraldehyde and the alkali liquid are fully contacted to carry out the condensation reaction. The reaction temperature in the condensation reactor 80 was set to 60° C., and the reaction pressure was set to 0.18 MPa.

The condensation reaction product is dispersed and broken by the external micro-bubble generator 110 and then enters the hydrogenation reactor 120. The reaction temperature in the hydrogenation reactor 120 is set to 60°C and the reaction pressure is set to 0.50MPa. The hydrogenation reaction product is rectified by the rectification tower 130 to obtain octanol.

After testing, after using the system and process, the conversion rate of propylene is 98.5%, the conversion rate of butyraldehyde is 97.2%, and the synthesis efficiency of the process is increased by 4.3%.

Example 2

The production system of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the reaction temperature in the carbonyl reactor 10 is set to 88°C, and the reaction pressure is set to 1.1MPa; the reaction temperature in the condensation reactor 80110 is set to 65°C °C, the reaction pressure is set to 0.21 MPa; the reaction temperature in the hydrogenation reactor 120 is set to 70 °C, and the reaction pressure is set to 0.70 MPa.

After testing, after using the system and process, the conversion rate of propylene is 99.0%, the conversion rate of butyraldehyde is 98.5%, and the synthesis efficiency of the process is increased by 4.5%.

Example 3

The production system of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the reaction temperature in the carbonyl reactor 10 is set to 95° C., and the reaction pressure is set to 1.3 MPa; the reaction temperature in the condensation reactor 80 is set to 70° C. °C, the reaction pressure is set to 0.25 MPa; the reaction temperature in the hydrogenation reactor 120 is set to 78 °C, and the reaction pressure is set to 0.80 MPa.

After testing, after using the system and process, the conversion rate of propylene is 99.3%, the conversion rate of butyraldehyde is 99.0%, and the synthesis efficiency of the process is increased by 5.0%.

In a word, compared with the production system of propylene carbonylation to produce octanol in the prior art, the production system of the present invention has high material conversion rate, low energy consumption, low cost, high safety, low required reaction temperature and pressure, and side reactions. It is worthy of widespread application.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

1. A system for producing octanol, comprising: a carbonyl reactor and a butyraldehyde separation device; the carbonyl reactor is connected with the butyraldehyde separation device; the butyraldehyde separation device is provided with a n-butyraldehyde outlet , the n-butyraldehyde outlet is connected with a condensation reactor, a first reboiler and a first pre-disperser are arranged between the condensation reactor and the butyraldehyde separation device, and the gas phase outlet of the first reboiler and the liquid phase outlet are both passed into the first predispersor; the n-butyraldehyde separated by the butyraldehyde separation device flows out from the n-butyraldehyde outlet, and passes through the first reboiler and the first reboiler. A pre-disperser is dispersed into n-butyraldehyde bubbles and passed into the condensation reactor;

   A micro-interface generator is arranged in the condensation reactor, and the micro-interface generator is connected with the first pre-disperser to further disperse the n-butyraldehyde bubbles into micro-level micro-bubbles; the condensation reactor A rotating shaft is arranged longitudinally inside, and the rotating shaft penetrates the bottom of the condensation reactor and is connected with a motor; the part of the rotating shaft located in the condensation reactor is provided with a plurality of stirring paddles; the top of the rotating shaft is connected with distribution disk; the distribution disk is arranged at the outlet of the micro-interface generator;

   The distribution disk is conical; a plurality of guide holes are evenly distributed on the distribution disk to evenly distribute the micro-bubbles generated by the micro-interface generator;

   The material outlet of the condensation reactor is connected with a hydrogenation reactor, a second reboiler and an external microbubble generator are arranged between the hydrogenation reactor and the condensation reactor, and the condensation reactor generates The octenal is divided into a gas-phase stream and a liquid-phase stream through the second reboiler, and the gas-phase stream and the liquid-phase stream are all passed into the external microbubble generator, and in the external microbubble generator After being dispersed into micron-sized octenal microbubbles, flow into the hydrogenation reactor;

   The hydrogenation reactor is provided with a built-in micro-bubble generator, and the built-in micro-interface generator is connected with the hydrogen cylinder; a second pre-disperser is arranged between the hydrogen cylinder and the built-in micro-interface generator , the second pre-disperser is located outside the hydrogenation reactor; after the hydrogen is dispersed into hydrogen bubbles by the second pre-dispersor, it is again dispersed into micron-scale hydrogen micro-bubbles inside the built-in micro-interface generator.
2. The octanol production system according to claim 1, wherein the first pre-dispersor and the second pre-disperser are both provided with a multi-layer dispersion layer, and the dispersion layer is composed of a plurality of different diameters. of circular granules piled up.
3. The octanol production system according to claim 1, wherein the side wall of the condensation reactor is provided with a liquid injector for injecting lye, the liquid injector comprising a semicircular injector body and The spray head is evenly arranged on the semicircular surface of the sprayer main body; the liquid sprayer is located below the micro-interface generator along the vertical direction; the liquid sprayer is connected with a lye storage tank.
4. The system for producing octanol according to claim 1, wherein the hydrogenation reactor is provided with two bubble distributors with opposite outlets, and the bubble distributor located above and the built-in micro-bubble generate The air bubble distributor located below is connected to the external micro-bubble generator.
5. The octanol production system according to claim 4, wherein the bubble distributor comprises a distributor main body and a plurality of nozzles; and the plurality of nozzles are obliquely arranged on the distributor main body to distribute the micro-bubbles evenly dispersion.
6. The system for producing octanol according to claim 1, wherein a propylene inlet and a synthesis gas inlet are sequentially arranged on the side wall of the carbonyl reactor; An interface generator, the micro-interface generator located above is connected to the propylene inlet, and the micro-interface generator located below is connected to the synthesis gas inlet.
7. The octanol production system according to claim 6, wherein the bottom of the carbonyl reactor is provided with a solvent inlet; the side wall of the carbonyl reactor is also provided with a catalyst injector, the catalyst injector It is arranged between the two micro-interface generators in the vertical direction.
8. The octanol production system according to claim 6, wherein the carbonyl reactor, the condensation reactor, the hydrogenation reactor and the second hydrogenation reactor are all connected with a supplementary Catalyst circulation device for catalysts.
9. The method for preparing octanol using the production system of octanol described in any one of claims 1-8, is characterized in that, comprises the steps:

   Propylene and synthesis gas are mixed with catalyzer, carry out hydroxyl synthesis reaction, obtain thick product after defoaming again, and thick product obtains n-butyraldehyde through separation;

   After the n-butyraldehyde is broken by the micro-interface, it is subjected to a condensation reaction with the lye to generate octenal, and the octenal and hydrogen are respectively subjected to micro-interface fragmentation, and the crude octanol product is obtained after the hydrogenation reaction, and the crude octanol product is obtained. The product octanol is obtained after rectification and purification.
10. The method according to claim 9, wherein the reaction temperature of the hydroxyl synthesis is 80-95°C, and the pressure is 0.8-1.3MPa; preferably, the catalyst is a rhodium catalyst; preferably, the hydrogenation reaction The reaction temperature in the vessel is 60-78°C, and the reaction pressure is 0.50-0.80MPa.

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