A process for the production of aliphatic carboxylic acids and apparatus therefor

Abstract

The present application relates to a kind of production aliphatic carboxylic acid and its device, using the lower spray liquid jet loop reactor with two-stage nozzle as reaction device, in the presence of liquid inorganic acid catalyst, by catalyst water, make olefin, carbon monoxide and water carry out one-step reaction, continuously prepare carboxylic acid.The reaction product of the present application is separated and purified, and aliphatic carboxylic acid product is obtained, and the recovered catalyst solution is returned to the reaction system for recycling, to realize closed loop, no large amount of waste acid is generated, which greatly reduces the environmental burden.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic carboxylic acid synthesis, and particularly relates to an improved method for preparing aliphatic carboxylic acid by reacting olefin, carbon monoxide and water and a device thereof. BACKGROUND

[0002] It is known that carboxylic acid can be synthesized from olefin, carbon monoxide and water in the presence of an acidic catalyst. Although such a method has potential advantages of cheap and readily available raw materials and short reaction path, its industrial application still faces many challenges such as harsh reaction conditions, complex process flow, equipment corrosion and environmental pollution.

[0003] The development of such processes mainly experienced three stages: high-pressure one-step method, medium-pressure two-step method and low-pressure two-step method.

[0004] The early high-pressure one-step method process (such as Du Pont method) can achieve one-step synthesis, but it needs to be carried out at an extremely high temperature of 300-400°C and a pressure of 200-1000 atm, which requires strict requirements for the material of the reaction equipment and the catalyst is severely corroded, with limited yield and poor economic efficiency. For example, US1924766A discloses a method for preparing fatty acid by reacting olefin, carbon monoxide and water vapor, which achieves ideal results when the concentration of olefin in the total reactants is between 1.5% and 10% (by volume) and a pressure of 500 atm or higher is used, and the reaction can be carried out at 200°C to 500°C.

[0005] In order to further optimize the reaction conditions, US2831877A discloses a method for producing carboxylic acid by a medium-pressure two-step method, in which an olefin compound and carbon monoxide are contacted in a liquid phase in the presence of an essentially water-free acid catalyst, boron fluoride is added, and then water is added to the formed reaction mixture to obtain carboxylic acid by hydrolysis. The reaction pressure is not more than 100 atm. The temperature is not more than 100°C. Although this method alleviates the need for high pressure, it still requires additional corrosion-resistant hydrolysis equipment, and a large amount of water needs to be removed during the catalyst recovery process, which is complex and costly.

[0006] In the 1970s, Y. Souma et al. of Japan proposed a two-step reaction for synthesizing carboxylic acid under low pressure (Bulletin of the Chemical Society of Japan, Vol. 47, No. 7, July 1974, pp. 1717-1719). However, this process still has the disadvantages of high acid consumption, difficulty in separating the product, severe equipment corrosion and environmental pollution, which to some extent limits the industrialization process of the process.

[0007] In the low-pressure two-step method, the catalyst precursor (such as cuprous oxide) needs to react with carbon monoxide in strong acid to form a carbonyl copper complex. This process is a gas-liquid-solid heterogeneous reaction, and the mass transfer resistance is large. The solubility of carbon monoxide in acid solution is low, and cuprous oxide is easy to agglomerate and difficult to disperse effectively, resulting in low reaction efficiency. The existing technology generally uses high-speed stirring to strengthen mass transfer, but there are still problems such as high energy consumption, serious equipment wear, and long reaction period. Chinese patent CN105688759B discloses a centrifugal inner cyclone type multiphase jet reactor and its method for preparing tertiary carbonic acid. The upper end of the reactor is a cylinder, and the lower end is a conical body connected to the cylinder reactor. The bottom of the conical body reactor is connected to a liquid tank connected to the cylinder. The ultra-fine cuprous oxide powder is added to the reactor in the form of a CO gas suspension sol, and the cuprous oxide suspension particles are mixed and reacted to form a multi-carbonyl copper compound under the action of liquid strong acid in the form of a thin film jet, and further react with olefins to prepare tertiary carbonic acid. The above method is still a two-step method, although it overcomes the problem of agglomeration of cuprous oxide powder mixed with liquid acid in traditional kettle process, and improves the reaction yield, but the waste acid containing cuprous oxide after dilution is difficult to reuse, and a large amount of hazardous waste is generated; the reaction process and reactor are complex, and the recovery of unreacted CO for recycling is prone to CO leakage.

[0008] In view of the above problems, it is still necessary to develop a more efficient, safe and environmentally friendly carboxylic acid synthesis process, which can realize continuous reaction under mild conditions, avoid the use of solid catalysts, reduce acid consumption, simplify product separation, and fundamentally solve the problems of equipment corrosion and environmental pollution. SUMMARY

[0009] The purpose of the present application is to overcome the defects in the existing carboxylic acid production process, and to provide a method and device for producing carboxylic acid with mild reaction conditions, low energy consumption, environmental friendliness and easy industrial continuous production.

[0010] To achieve the above purpose, the technical solution adopted by the present application is as follows: a lower spray type liquid jet loop reactor is used as the core reaction device, and olefins, carbon monoxide and water are reacted in the presence of a liquid inorganic acid catalyst to continuously produce carboxylic acid.

[0011] The production method of the present application comprises the following steps:

[0012] (a) A liquid inorganic acid catalyst carrying reaction water is added to a downward-spraying liquid jet circulating reactor, wherein the amount of reaction water is at least sufficient to react stoichiometrically with the olefin to be reacted; carbon monoxide gas is introduced into the gas phase space above the reactor and maintained at a certain pressure, preferably the partial pressure (reaction pressure) of carbon monoxide gas is 0.1-10 MPa, more preferably 1-5 MPa; the reactor is equipped with a flow guide tube and a flow guide plate; the molar ratio of the amount of carbon monoxide introduced to the amount of carbon monoxide theoretically consumed in the reaction is greater than 3:1; the liquid inorganic acid catalyst is sulfuric acid, boron trifluoride, or a complex of boron trifluoride and sulfuric acid / phosphoric acid, preferably the inorganic acid catalyst contains at least boron trifluoride or boron trifluoride dihydrate, wherein the molar ratio of boron trifluoride to olefin is 0.5-5:1;

[0013] (b) Establishing a circulation loop: The solution in the liquid phase space of the reactor is extracted by a circulation pump, and after the temperature is controlled by a heat exchanger, it is delivered to the two-stage injection nozzles at the top of the reactor;

[0014] (c) C2-C 24 The olefin is injected into the circulation loop via a metering pump and mixed with the circulating solution therein; the molar ratio of the reaction water to the olefin is 1-1.15:1; in some embodiments, the olefin is isobutylene, dimer isobutylene, or C6-C... 15 propylene oligomers (propylene oligomers);

[0015] (d) The mixed material is ejected through the first-stage nozzle, and the resulting negative pressure automatically draws carbon monoxide gas from the gas phase space of the reactor into the second-stage nozzle. In the second-stage nozzle, the gas and liquid phases mix and react to generate aliphatic carboxylic acids. The liquid flow rate in the first-stage nozzle is 15-35 m / s, preferably 24-30 m / s. The controlled temperature is 0℃-100℃, and the reaction time is 0.1-10 hours, preferably 30℃-60℃, and the reaction time is 0.2-1 hours.

[0016] (e) The reacted material flows downward into the guide tube, impacts the guide plate, and then changes direction, flowing upward along the annular gap between the guide tube and the inner wall of the reactor to form a circulation for complete reaction; the annular gas content between the inner wall of the reactor and the guide tube is 8%-15%, preferably 9-11%;

[0017] (f) Discharge the reaction products containing aliphatic carboxylic acids and catalyst; perform separation and purification to obtain aliphatic carboxylic acid products, and return the recovered catalyst solution to the reaction system for recycling.

[0018] In the down-spray liquid jet loop reactor, the liquid inorganic acid catalyst carries the reaction water in a molar ratio of 1-1.15:1 with the olefin to be reacted to participate in the reaction, so that the catalyst is not additionally diluted while providing the required water for the reaction and catalyzing the reaction of the olefin and CO, thereby ensuring its activity and concentration, and the catalyst after the reaction can be completely reused without complex treatment, fundamentally solving the environmental protection problem of a large amount of waste acid generated in the traditional two-step method. This ingenious catalyst system design makes a reaction essentially containing catalyst activation and carbonylation two steps, which embodies the continuous characteristics of one-step method in process flow.

[0019] Further, the present application provides a device for producing aliphatic carboxylic acid in the above method, comprising:

[0020] A reaction unit comprising a down-spray liquid jet loop reactor, the reactor is internally provided with a hollow cylindrical draft tube and a draft plate, the top of which is arranged with a first-stage nozzle and a second-stage nozzle from top to bottom, forming two-stage jet nozzles; a carbon monoxide inlet is provided between the first-stage nozzle and the second-stage nozzle; an annular gap channel is formed between the outer wall of the draft tube and the inner wall of the reactor body, and the jet direction of the second-stage nozzle is towards the inner space of the draft tube; the draft plate is located directly below the draft tube and is configured to change the flow direction of the intercepted material from vertical downward to the annular gap channel;

[0021] A catalyst circulation unit comprising a circulation pump, a heat exchanger and a material circulation pipeline, the inlet of the circulation pump is in communication with the reaction product outlet at the bottom of the reactor, and the heat exchanger is provided on the material circulation pipeline and connected to the first-stage nozzle;

[0022] An olefin feed unit comprising an olefin feed pipeline and a metering pump, the olefin feed pipeline is connected to the material circulation pipeline in the catalyst circulation unit between the outlet of the circulation pump and the inlet of the heat exchanger;

[0023] A carbon monoxide feed unit comprising a carbon monoxide inlet device in communication with the upper part of the reactor;

[0024] A separation and purification unit comprising a water washing tower, the material inlet at the bottom of which is connected to the reaction product outlet of the reactor; and the catalyst solution outlet at the bottom is connected to the catalyst circulation unit.

[0025] In some embodiments, the separation and purification unit further comprises a recovery tower and a desolvation tower, the recovery catalyst solution outlet of the water washing tower is connected to the catalyst circulation unit and the recovery tower for concentrating the catalyst solution, respectively, the concentrated catalyst solution outlet of the recovery tower is connected to the catalyst circulation unit, and the water removal outlet is connected to the water washing tower.

[0026] The inventors have unexpectedly found that, by using a downwardly spraying liquid jet loop reactor and matching specific process conditions, the high yield of the low-pressure two-step process can be combined with the advantages of mild conditions, and the process simplicity and single equipment of the one-step process.

[0027] The downwardly spraying liquid jet loop reactor used in the present application can achieve extremely high mixing and mass transfer efficiency at relatively low energy consumption. The working principle is that the high-speed flowing liquid phase is used to desuck, shear and disperse the gas phase through two-stage nozzles, so that the phases are fully mixed, thereby greatly increasing the phase interface contact area, producing an effect similar to vigorous stirring to promote reaction completion. Compared with the traditional mechanical agitated tank reactor, the mixing is achieved by fluid kinetic energy rather than mechanical energy, the energy consumption is significantly reduced, and the mixing is more rapid and uniform.

[0028] Compared with the existing high-pressure one-step process, medium-pressure and low-pressure two-step process, the present application has the following advantages: ① The present application can efficiently and in high yield prepare carboxylic acid under low pressure and mild conditions without the participation of solid catalyst; by using catalyst-carrying water, controlling water addition amount and jet reaction, coupling into a one-step process, without separate hydrolysis, and making the catalyst fully recovered and utilized, no large amount of waste acid is generated, and the environmental burden is greatly reduced; ② The present application uses a process of nozzle+internal circulation+external circulation to make the reaction efficiency high, the energy consumption low, the amount of catalyst relative to the olefin small, the time short, and the reaction conditions mild, and when the reaction temperature is controlled within a certain range, there is no need to use low-temperature water for heat exchange; ③ The jet loop reactor used in the present application has no stirring transmission device, the system is closed, the complex hydrolysis of the traditional two-step process is avoided, it is easy to anticorrosion on the inner wall, the maintenance amount of the reactor is small, the service life is long, and the equipment investment and operation cost are significantly reduced; ④ CO gas is automatically sucked into the reaction zone by the Venturi effect to realize closed loop circulation, avoiding the leakage risk that may be caused by gas compression circulation in the traditional process; ⑤ The present application can realize external heat exchanger to adapt to the working condition of a large amount of heat release in the carbonylation process, and keep the reaction temperature constant. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The production device connection schematic diagram of the aliphatic carboxylic acid in the embodiment of the present application;

[0030] Figure 2 The structure schematic diagram of the jet loop reactor in the embodiment of the present application.

[0031] It should be noted that the meanings of the reference numerals in the attached figures are as follows: 1: Reactor; 2: Flow guide tube; 3: Flow guide plate; 4: First-stage nozzle; 5: Second-stage nozzle; 6: Annular channel; 7: Gas inlet; 8: Reaction product outlet; 9: Circulation pump; 10: Heat exchanger; 11: Material circulation pipeline; 12: Catalyst feed pipeline; 13: Carbon monoxide inlet device; 14: Olefin feed pipeline; 15: Water washing tower; 16: Reaction product outlet pipeline; 17: Water inlet pipeline; 18: Catalyst recovery tower; 19: Solvent removal tower; 20: Solvent feed pipeline. Detailed Implementation

[0032] To provide a more comprehensive understanding of the present invention, the production process of aliphatic carboxylic acids is described below by way of example.

[0033] Please see Figure 1 and Figure 2 The diagram shows the connection of the production equipment and the structural diagram of the jet circulation reactor. The aliphatic carboxylic acid production equipment of the present invention includes a reaction unit, a carbon monoxide feeding unit, a catalyst circulation unit, an olefin feeding unit, and a separation and purification unit. The reaction unit includes a down-spray liquid jet circulation reactor 1. The reactor body has a cylindrical inner wall. Inside, there is a guide tube 2 and a guide plate 3. The first-stage nozzle 4 and the second-stage nozzle 5 arranged from top to bottom on the top of the guide tube 2 constitute a two-stage jet nozzle. The hollow cylindrical guide tube 2 is coaxially sleeved inside the reactor body. An annular channel 6 is formed between the outer wall of the guide tube 2 and the inner wall of the reactor body. The outlet of the second-stage nozzle 5 is located inside the guide tube 2, and its spray direction is towards the inner space of the guide tube 2. The guide plate 3 is located directly below the guide tube 2 and is configured to change the flow direction of the intercepted material from vertically downward to towards the annular channel 6. In this embodiment, the guide plate 3 is in the shape of an inverted cone. The gas-liquid mixture flowing out from the lower outlet of the guide tube 2 impacts the guide plate 3, and after the flow direction is changed by the guide plate 3, it enters the annular channel 6 and flows upward, thus forming a circulating flow path inside the guide tube 2 and between the annular channel 6. A carbon monoxide inlet 7 is provided between the first-stage nozzle 4 and the second-stage nozzle 5. The upper part of the reactor 1 is connected to the carbon monoxide feeding unit, and the bottom is provided with a reactant outlet 8.

[0034] The catalyst circulation unit includes a circulation pump 9, a heat exchanger 10, and a material circulation pipeline 11. The inlet of the circulation pump 9 is connected to the reactant outlet 8 at the bottom of the reactor 1, and the outlet is connected to the material circulation pipeline 11. After passing through the heat exchanger 10, it is connected to the inlet of the first-stage nozzle 4. The inorganic acid catalyst carrying the reaction water enters the material circulation pipeline 11 through the catalyst feed line 12. The circulation pump 9 can be a corrosion-resistant shielded pump, which continuously draws the liquid phase material at the bottom of the reactor from the reactant outlet 8, adjusts it to the required reaction temperature through the heat exchanger 10, and then delivers it to the two-stage nozzle system at the top of the reactor 1.

[0035] Carbon monoxide feed unit, comprising a carbon monoxide inlet 13, which is in communication with the upper gas space of the reactor 1; carbon monoxide gas is fed into and maintained at a pressure in the reactor 1 by a compressor.

[0036] Olefin feed unit, comprising an olefin feed line 14, which is connected to the material circulation pipe 11 in the catalyst circulation unit between the outlet of the circulation pump 9 and the inlet of the heat exchanger 10; an olefin containing 2 to 24 carbon atoms is pumped into the material circulation pipe 11 through the olefin feed line 14 by a metering pump (not shown in the figure) for accurate metering, mixed with the circulating catalyst solution, and then enters the first stage nozzle 4. When the above-mentioned mixed material is sprayed out of the first stage nozzle 4, a negative pressure (Venturi effect) is generated in the chamber between the first stage nozzle 4 and the second stage nozzle 5, so that the CO gas in the upper space of the reactor 1 is automatically sucked into the second stage nozzle 5 through the gas inlet 7. The gas-liquid mixed material is highly sheared and dispersed inside and at the outlet of the second stage nozzle 5, achieving extreme mixing and mass transfer, so that most of the olefins are instantaneously converted into carboxylic acids. Subsequently, the gas-liquid mixed material enters a draft tube 2 located in the center of the reactor 1 to further enhance the intensity of the circulation. The mixed material moves downward along the draft tube 2, impacts the specially designed inverted conical guide plate 3 at the bottom, turns and flows upward from the annular gap channel 6 between the draft tube 2 and the inner wall of the reactor 1, completing a strong internal circulation process. In this process, the unreacted olefins, CO, water and catalyst are fully contacted and continue to react, thereby increasing the olefin conversion rate to a very high level.

[0037] When the reaction proceeds to the point where the reaction water carried by the catalyst is substantially consumed (i.e., converted into carboxylic acid), the continuous production mode can be entered: new olefins and liquid inorganic acid catalyst supplemented with reaction water are continuously fed into the catalyst circulation loop, while the reaction product (i.e., the mixture of carboxylic acid and catalyst) is discharged from the bottom of the reactor 1.

[0038] Separation and purification unit, comprising a water washing tower 15, the bottom of which is in communication with the reaction product outlet 8 of the reactor 1 through a reaction product discharge line 16; the bottom of the catalyst solution outlet is in communication with the catalyst circulation unit. The reaction product discharged from the reactor 1 enters the water washing tower 15 and is countercurrently extracted and washed with an equal amount of water introduced through a water inlet line 17. Then, the purified carboxylic acid product is obtained from the top of the water washing tower 15, while the recovered catalyst solution from the bottom of the water washing tower, which has been re-carried with reaction water, can be returned to the reaction system for recycling, thereby realizing the closed-loop circulation of the catalyst and the continuous reaction. In some embodiments, the above-mentioned recovered catalyst solution is first sent to a catalyst recovery tower 18 through a line for concentration, the excess water removed is used for water washing in the water washing tower 15, and the concentrated catalyst is returned to the reactor 1 through the catalyst feed line 12.

[0039] In some embodiments, a hydrocarbon solvent can be added to the reaction. The hydrocarbon solvent is fed into the reactor 1 through the solvent feed line 20 via the material circulation pipe 11 to facilitate the separation of the carboxylic acid product from the regenerated catalyst. The carboxylic acid product dissolved in the solvent is separated from the solvent in the water wash column 15 and then enters the desolventizer 19 to achieve the separation of the product from the solvent. The recovered solvent is recycled into the reactor 1 through the solvent feed line 20, and the obtained crude carboxylic acid product is sent to a subsequent purification process (if a higher purity product is required).

[0040] In the above production device, the fluid connection between each device is achieved by the configured pipe, valve and pumping unit, etc. The type and setting mode of the pipe, valve (such as ball valve, stop valve, regulating valve), conveying device (such as centrifugal pump, metering pump), actuator and instrument required by the production device are the known suitable solutions in the prior art, and can be routinely selected and set according to the process requirements (such as flow, pressure, temperature, medium characteristics) to ensure that the materials are transmitted and controlled between the reaction devices in the predetermined order, flow and condition.

[0041] Regarding the reaction process, the raw material olefin and the inorganic acid catalyst carrying additional reaction water enter the circulation pipe 11, and after heat exchange to reach the reaction temperature, they pass through the first-stage nozzle 4 and are injected into the second-stage nozzle 5. At this time, a pressure difference is generated between the first-stage nozzle and the second-stage nozzle, and carbon monoxide is sucked in through the gas inlet 7, mixed with the entering liquid material and reacted to generate a hydrolysable intermediate reaction product, the chemical reaction of which is shown as follows:

[0042]

[0043] wherein, represents an acid anion. When the intermediate reaction product contacts with the almost equimolar amount of additional water carried by the catalyst, a hydrolysis reaction occurs rapidly, releasing the target carboxylic acid product and regenerating the acid catalyst:

[0044]

[0045] As mentioned above, the reaction of the olefin and the carbon monoxide in the presence of the acid catalyst does not require high temperature and high pressure. The reaction conditions suitable for the present application are listed in Table 1.

[0046] Table 1 Reaction conditions

[0047]

[0048] The reaction pressure listed in Table 1 is expressed as carbon monoxide partial pressure. In actual production, either pure carbon monoxide gas or a CO-containing synthesis gas can be used, as long as the set carbon monoxide partial pressure can be reached in the reactor. It should be noted that if harmful acidic components (such as sulfides, carbon dioxide, oxygen, or metal carbonyl compounds) are present in the raw material gas, they must be removed before feeding; inert impurities (such as hydrogen, methane, nitrogen) have no negative effect on the reaction and are allowed to exist. In the embodiments of the present application, CO is input into the jet loop by a compressor, the CO partial pressure in the reactor needs to be kept constant, and the supply of pure carbon monoxide should be significantly excessive to the stoichiometric demand for reaction with olefins, and the molar ratio of pure CO to the CO required for the reaction should be greater than 3. The relationship between the CO suction amount in the nozzle and the liquid flow through the nozzle can be determined by simulation experiments on the nozzle.

[0049] The olefins fed into the reactor need to be in liquid state under reaction conditions, and are usually linear or branched olefins containing 2-24 carbon atoms and mixtures thereof. Suitable examples include ethylene, propylene, butene, isobutylene, pentene, decene, hexadecene, octadecene, etc. Among them, C4-C 15 Olefins, especially propylene, are polymerized to form C6-C 15 The branched olefins are the preferred raw materials, because the tertiary carbonic acid generated thereby can be derived into high-stability esters, such as the key component of synthetic lubricating oil, and can be prepared into tertiary carbonic acid vinyl ester, tertiary carbonic acid glycidyl ester, etc. tertiary carbon monomers, thereby preparing tertiary carbon emulsion and tertiary carbon resin polymers, which are widely used in the fields of coating, bonding and adhesion, and are ideal materials for preparing high-performance ultra-low VOC coatings, adhesives and composites.

[0050] The liquid inorganic acid catalyst used in the present application needs to satisfy the density > 1.25 g / cm³, preferably ≥ 1.35 g / cm³, and best 1.5-1.85 g / cm³, to ensure the internal circulation in the reactor. Suitable acids include sulfuric acid, boron trifluoride dihydrate (BF3·2H2O, density about 1.6 g / cm³) and a composite of boron trifluoride and sulfuric acid / phosphoric acid. Among them, boron trifluoride dihydrate is the best choice due to its high catalytic activity for branched high molecular weight olefins, and its preparation method can be: passing BF3 gas into vigorously stirred water ≤ 20 ℃ until 0.5 mol of BF3 is absorbed per mol of water. The preparation of other BF3-containing catalysts is by passing BF3 into 85% phosphoric acid or 85% sulfuric acid at 100 ℃ until 0.75-1.5 mol of BF3 is absorbed per mol of acid. When sulfuric acid is used alone, the concentration of sulfuric acid is usually above 90%.

[0051] A typical catalyst system is shown in Table 2:

[0052] Table 2 Composition and density of liquid inorganic acid catalyst

[0053]

[0054] The present application adopts a specific jet loop reactor, which needs to meet two conditions, one is that the negative pressure generated between the first stage nozzle and the second stage nozzle can absorb pure CO equivalent or more than the molar number of the simultaneously entering olefins, the other is that the liquid flow rate of the first stage nozzle must be large enough to give the loop flow in the reactor sufficient kinetic energy. In the present application, the liquid flow rate of the first stage nozzle is 15-35 m / s, preferably 20-30 m / s, more preferably 24-30 m / s.

[0055] Liquid flow rate of the first stage nozzle = 4 x liquid circulation flow rate / (first stage nozzle diameter square x π)

[0056] The annular gap gas holdup between the reactor inner wall and the draft tube of the jet loop reactor is an important indicator, high annular gap gas holdup not only represents sufficient gas-liquid reaction, but also indicates less gas-liquid back mixing, more similar to plug flow reaction. But too high gas holdup is also not conducive, which will lead to coalescence of gas bubbles, making the gas bubble size larger, reducing the gas-liquid contact area, affecting the progress of gas-liquid mass transfer reaction. Therefore, the annular gap gas holdup of the loop reactor is in the range of 10-15%, preferably 12-14%, more preferably 9-11%.

[0057] The annular gap gas holdup is obtained by the following method:

[0058] Referring to Figure 2 , two points A and B vertically on the same line are arranged on the wall of the loop reactor, the height difference of the two points is ΔH. First, after the batch reaction is completed, before the continuous reaction is carried out, the static pressure difference of the two points is measured as ΔP0 under the condition that the circulating pump is stopped, ΔP0 = ρ0ΔH. Then, when the continuous reaction is carried out, under the condition that the circulating pump is continuously working and CO is continuously absorbed, the dynamic pressure difference of the two points is measured as ΔP n , ΔP n = ρ n ΔH. Wherein ρ is the density of the reaction liquid between the reactor inner wall and the draft tube. From this, we can derive:

[0059] ρ n / ρ0=ΔP n / ΔP0

[0060] ρ n / ρ0=(W 气n +W 液n / V) / W 液0 / V=ΔP n / ΔP0

[0061] And W 气n is much smaller than W 液n , which can be ignored:

[0062] ρn / ρ0=W 液n / W 液0 =ΔP n / ΔP0

[0063] then the annular gap gas holdup ε n =1-W 液n / W 液0 =1-ΔP n / ΔP0

[0064] Therefore, by measuring the pressure difference ΔP of two vertical points of the reactor, the annular gap gas holdup ε n of the jet loop reactor in continuous reaction can be determined.

[0065] The following examples use the production method and device of the present application to prepare carboxylic acid, wherein the structural parameters of the jet loop reactor 1 used are: the diameter of the first stage nozzle is 4 mm, the diameter of the jet loop reactor 1 is 200 mm, the height is 700 mm, and other structural data are based on this. In actual production, the structural parameters of the reactor can be designed according to production needs. In this example, the height of the gas-liquid reaction mixture of the jet loop reactor is set to 550 mm, and the liquid level is controlled by a liquid level meter and a circulating pump discharge. The volume of the gas-liquid reaction mixture at this height is 21 liters. The reaction feed temperature is kept constant by adjusting the flow rate of the cold and hot media of the circulating heat exchanger. The gas phase pressure of the reactor is kept constant by supplementing the amount of CO through a compressor. In a specific example, the gas flow rate sucked by the second stage nozzle is substantially equal to the liquid flow rate entering the first stage nozzle. The reaction liquid level is maintained by controlling the bottom circulating pump discharge. The feed speed of the first stage nozzle is adjusted to the desired value by adjusting the circulating pump and feed flow rate, and the amount of annular gap gas holdup is adjusted to the set value by this flow rate.

[0066] Example 1

[0067] In this example: the catalyst is BF3·2H2O (molecular weight is 103.84, density is 1636 kg / m 3 ), the olefin is tripropylene (molecular weight is 126, density is 740 kg / m 3 ), and the product is neodecanoic acid (molecular weight is 172.26, density is 910 kg / m 3 ); the catalyst: olefin: catalyst-carrying reaction water: water washing tower washing water = 5:1:1:1 (molar ratio); the circulating pump flow rate is 1 m 3 / h, the head is 0.5 Mpa, the liquid linear speed of the first stage nozzle is 22 m / s; the CO flow rate sucked by the nozzle is 0.8 m 3 / h, the molar ratio of CO to olefin is 8.9:1; the annular gap gas holdup is 8%; the reaction pressure is 10 Mpa, the reaction temperature is 20℃, and the reaction retention time is 0.1 hour.

[0068] ① Initial reaction (start-up)

[0069] The catalyst 19.74 kg and the reaction water 0.68 kg were added into the jet loop reactor, the gas phase was replaced by CO, and the pressure was increased to 10 MPa, and during the reaction, CO was continuously introduced to maintain the pressure stable during the reaction. The circulation pump was started, and the circulation pump liquid flow rate was 1 m 3 / h, of which the flow rate of the reaction liquid drawn from the bottom of the reactor was 935 l / h, and the flow rate of the olefin added into the circulating reaction liquid by the metering pump was 65 l / h. The circulating reaction liquid and the added olefin were mixed on the circulation loop and heat exchanged by the heat exchanger, so that the temperature of the liquid entering the reaction nozzle and the loop reactor was 20°C. The olefin and CO and the reaction water reacted in the presence of the catalyst in the nozzle and the loop reactor for 0.1 hour.

[0070] ② Continuous reaction

[0071] After the intermittent reaction was completed, the continuous feeding was started. The circulation pump flow rate was 1 m 3 / h, of which the circulation flow rate of the reaction liquid drawn from the bottom of the reactor was 808 l / h, the olefin was added into the circulating reaction liquid by the metering pump at a flow rate of 64.7 l / h, and the catalyst carrying reaction water was added at a flow rate of 127.5 / h (of which the catalyst was 120.7 l / h, and the reaction water carried was 6.8 l / h). When the reaction material height exceeded the set liquid level height, which was 550 mm in this example, the catalyst and the mixture of neodecanoic acid were discharged from the bottom of the reactor to maintain the liquid level constant at 550 mm. The mixture was then introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water was introduced into the water washing tower from the bottom at a flow rate of 6.8 l / h, the crude carboxylic acid overflowed from the top of the water washing tower, and the catalyst carrying reaction water was recovered from the bottom. The catalyst carrying reaction water was continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, and the crude carboxylic acid 4709 kg was collected, and the neodecanoic acid 4585 kg was obtained by rectification. It was calculated that:

[0072] ① Initial reaction olefin addition amount = olefin addition flow rate × retention time × olefin density = 65 L / h × 0.1 h × 0.74 kg / L = 4.79 kg

[0073] ② Continuous reaction olefin addition amount = olefin addition flow rate × reaction time × olefin density = 64.7 L / h × 72 h × 0.74 kg / L = 3449.34 kg

[0074] ③ Total reaction olefin addition amount = ① + ② = 3454.13 kg

[0075] ④ Total moles of reaction olefin addition amount = ③ / molar mass of olefin = 3454.13 kg / 126 = 27.41 kmol

[0076] ⑤ Theoretically, the yield of neodecanoic acid = ④ × molar mass of neodecanoic acid = 27.41 × 172.26 = 4722 kg

[0077] ⑥ Neodecanoic acid yield = Amount of neodecanoic acid obtained from distillation / ⑤ = 4585 / 4722 = 97.1%

[0078] The yield was 97.1%.

[0079] Example 2

[0080] In this embodiment: the catalyst is BF3·2H2O (molecular weight 103.84, density 1636 kg / m³). 3 The olefin is tripropylene (molecular weight 126, density 740 kg / m³), and the product is neodecanoic acid (molecular weight 172.26, density 910 kg / m³). 3 The molar ratio of catalyst: olefin: catalyst-carrying reaction water: water washing tower wash water is 3:1:1:1; the circulation pump flow rate is 1.1 m³ / s. 3 The flow rate is 1.15 m³ / h, the head is 0.5 MPa, and the liquid linear velocity in the first-stage nozzle is 24 m / s; the CO flow rate drawn in by the nozzle is 1.15 m³ / h. 3 / h, CO to olefin molar ratio of 9.2:1; annular gas holdup of approximately 9%; reaction pressure of 5 MPa, reaction temperature of 30 °C, and reaction retention time of 0.2 hours.

[0081] ① Initial reaction (driving)

[0082] 15.64 kg of catalyst and 0.9 kg of reaction water were added to the jet circulation reactor. The gas phase was replaced with CO, and the pressure was increased to 5 MPa. During the reaction, CO was continuously introduced to maintain a stable pressure. The circulation pump was started, with a liquid flow rate of 1.1 m³ / s. 3 The flow rate includes 1057 L / h of reaction liquid extracted from the bottom of the reactor and 43 L / h of olefins added to the circulating reaction liquid via a metering pump. The circulating reaction liquid and the added olefins are mixed in the circulation loop and heat exchanged through a heat exchanger to maintain the liquid temperature entering the reaction nozzle and circulating reactor at 30°C. The olefins, CO, and reaction water react in the nozzle and circulating reactor under the action of a catalyst for 0.2 hours.

[0083] ② Continuous reaction

[0084] After the batch reaction, continuous feeding was started. The circulation pump flow was 1.1 m3 / h, of which the circulation flow of reaction liquid taken from the bottom of the reactor was 1004.9 l / h, the olefin was added to the reaction liquid circulation flow by a metering pump at 42.8 l / h, and the catalyst carrying reaction water was added at 52.3 l / h (of which the catalyst was 47.8 l / h and the reaction water was 4.5 l / h). When the reaction material height exceeded 550 mm, the catalyst and neodecanoic acid mixture was discharged from the bottom of the reactor to keep the liquid level constant at 550 mm. It was then introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water was introduced into the water washing tower from the bottom at 4.5 l / h, the crude carboxylic acid overflowed from the top of the water washing tower, and the catalyst carrying reaction water was recovered from the bottom. The catalyst carrying water was continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, and 3114 kg of crude carboxylic acid was collected, and 3037 kg of neodecanoic acid was obtained by rectification, with a yield of 97.3%.

[0085] Example 3

[0086] In this example: the catalyst was BF3·2H2O (molecular weight 103.84, density 1636 kg / m 3 ), the olefin was isobutene (molecular weight 56.11, density 587.9 kg / m 3 ), and the product was tert-pentanoic acid (molecular weight 102.13, density 889 kg / m 3 ); the catalyst: olefin: catalyst carrying reaction water: water washing tower washing water = 3:1:1:1 (molar ratio); the circulation pump flow was 1.1 m 3 / h, the head was 0.5 Mpa, and the liquid line speed of the first stage nozzle was 24 m / s; the CO flow rate sucked by the nozzle was 1.15 m 3 / h, and the CO and olefin molar ratio was 7.4:1; the annular gap gas content was about 9%; the reaction pressure was 5 Mpa, the reaction temperature was 30℃, and the reaction residence time was 0.2 hours.

[0087] ① Initial reaction (start-up)

[0088] The catalyst 19.5 kg and the reaction water carrying 1.13 kg were added to the jet loop reactor, the gas phase was replaced with CO, and the pressure was increased to 5 Mpa, and during the reaction, CO was continuously introduced to keep the pressure stable during the reaction. The circulation pump was started, and the liquid flow of the circulation pump was 1.1 m 3where the flow rate of the reaction liquid withdrawn from the bottom of the reactor is 1070 1 / h, and the flow rate of the olefin added to the circulating reaction liquid by the metering pump is 30 1 / h. The circulating reaction liquid and the added olefin are mixed on the circulating loop and heat exchanged by the heat exchanger, so that the temperature of the liquid entering the reaction nozzle and the loop reactor is 30°C. The olefin and CO and the reaction water are reacted in the presence of the catalyst in the nozzle and the loop reactor for 0.2 hours.

[0089] ② Continuous reaction

[0090] After the batch reaction is completed, continuous feeding is started. The circulating pump flow rate is 1.1 m 3 / h, the circulating flow rate of the reaction liquid withdrawn from the bottom of the reactor is 1004.9 1 / h, the olefin is added to the circulating flow of the reaction liquid by the metering pump at a flow rate of 29.9 1 / h, and the catalyst carrying reaction water is added at a flow rate of 65.2 1 / h (where the catalyst is 59.6 1 / h and the reaction water is 5.6 1 / h). When the height of the reaction material exceeds 550 mm, the catalyst and the neodecanoic acid mixture is discharged from the bottom of the reactor to maintain the liquid level at 550 mm. It is then introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water is introduced into the water washing tower from the bottom at a flow rate of 4.5 1 / h, the crude carboxylic acid overflows from the top of the water washing tower, and the catalyst carrying reaction water is recovered from the bottom. The catalyst carrying reaction water is continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction is carried out for 72 hours, 2302 kg of crude carboxylic acid is collected, and 2255 kg of trimethylacetic acid is obtained by rectification, with a yield of 97.7%.

[0091] Example 4

[0092] In this example: the catalyst is BF3 / 1.3H3PO4 / 1.3H2O (molecular weight 218.6, density 1650 kg / m 3 ), the olefin is tripropylene (molecular weight 126, density 740 kg / m 3 ), and the product is neodecanoic acid (molecular weight 172.26, density 910 kg / m 3 ); the catalyst: olefin: catalyst carrying reaction water: water washing tower washing water = 3:1:1:1 (molar ratio); the circulating pump flow rate is 1.1 m 3 / h, the head is 0.5 MPa, and the liquid line speed of the first stage nozzle is 24 m / s; the flow rate of CO sucked by the nozzle is 1.15 m 3 / h, the molar ratio of CO to olefin is 14.3:1; the annular gap gas content is about 9%; the reaction pressure is 5 MPa, the reaction temperature is 30°C, and the reaction residence time is 0.2 hours.

[0093] ① Initial reaction (start-up)

[0094] The catalyst 21.29 kg and the reaction water 0.58 kg were fed into the jet loop reactor, the gas phase was replaced by CO, and the pressure was increased to 5 MPa, and the pressure was kept stable during the reaction by continuously feeding CO. The circulating pump was started, and the circulating pump liquid flow rate was 1.1 m 3 / h, including the flow rate of the reaction liquid taken out from the bottom of the reactor was 1072.4 l / h, and the flow rate of the olefin added into the circulating reaction liquid by the metering pump was 27.6 l / h. The circulating reaction liquid and the added olefin were mixed on the circulating loop and heat-exchanged by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor was 30℃. The olefin and CO and the reaction water reacted in the presence of the catalyst in the nozzle and the loop reactor for 0.2 hours.

[0095] 2. Continuous reaction

[0096] After the intermittent reaction was completed, the continuous feeding was started. The circulating pump flow rate was 1.1 m 3 / h, including the circulating flow rate of the reaction liquid taken out from the bottom of the reactor was 1004.9 l / h, the olefin was added into the circulating flow of the reaction liquid by the metering pump at a flow rate of 27.6 l / h, and the catalyst carrying reaction water was added at a flow rate of 67.4 / h (including the catalyst 64.5 l / h, and the reaction water carrying 2.9 l / h). When the reactant material height exceeded 550 mm, the material was discharged from the bottom of the reactor to keep the liquid level constant at 550 mm, and the material was a mixture of the catalyst and the neodecanoic acid. It was then introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water was introduced into the water washing tower from the bottom at a flow rate of 2.92 l / h, the crude carboxylic acid overflowed from the top of the water washing tower, and the catalyst carrying reaction water was recovered from the bottom. The catalyst carrying reaction water was continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, and the crude carboxylic acid 2015 kg was collected, and the neodecanoic acid 1981 kg was obtained by rectification, with a yield of 98.1%.

[0097] Example 5

[0098] In this example: the catalyst was BF3·2H2O (molecular weight was 103.84, density was 1636 kg / m 3 ), the olefin was tripropylene (molecular weight was 126, density was 740 kg / m 3 ), and the product was neodecanoic acid (molecular weight was 172.26, density was 910 kg / m 3 ); the catalyst: olefin: catalyst carrying reaction water: washing water of the water washing tower = 1.25:1:1:1 (molar ratio); the circulating pump flow rate was 1.2 m 3 / h, the head was 0.5 MPa, and the liquid linear velocity of the first stage nozzle was 27 m / s; the CO flow rate sucked by the nozzle was 1.3 m 3The molar ratio of CO to olefin is 7.2:1; the gas holdup is about 10%; the reaction pressure is 2 MPa, the reaction temperature is 40°C, and the reaction retention time is 0.5 hour.

[0099] ① Initial reaction (start-up)

[0100] The catalyst 9.12 kg and the reaction water 1.26 kg are added into the jet loop reactor, the gas phase is replaced by CO, and the pressure is increased to 2 MPa. During the reaction, CO is continuously fed to maintain the pressure. The circulation pump is started, and the liquid flow rate of the circulation pump is 1.2 m 3 / h, including the flow rate of the reaction liquid taken out from the bottom of the reactor 1176.1 l / h, and the flow rate of the olefin added into the circulation reaction liquid by the metering pump 23.93 l / h. The circulation reaction liquid and the added olefin are mixed on the circulation loop and are heated by the heat exchanger, so that the temperature of the liquid entering the reaction nozzle and the loop reactor is 40°C. The olefin, CO and the reaction water react in the presence of the catalyst in the nozzle and the loop reactor for 0.5 hour.

[0101] ② Continuous reaction

[0102] After the batch reaction is completed, the continuous feeding is started. The circulation pump flow rate is 1.2 m 3 / h, including the circulation flow rate of the reaction liquid taken out from the bottom of the reactor 1162.4 l / h, the addition of the olefin into the circulation flow of the reaction liquid by the metering pump at 23.9 l / h, and the addition of the catalyst carrying reaction water at 13.7 l / h (including the catalyst 11.2 l / h and the reaction water 2.5 l / h). When the reaction material height exceeds 550 mm, the material is discharged from the bottom to keep the liquid level constant at 550 mm, and the discharged material is the mixture of the catalyst and the neodecanoic acid. The mixture is introduced into the lower part of the water washing tower for countercurrent extraction washing. The reaction water is introduced into the water washing tower from the bottom at 2.5 l / h, the crude carboxylic acid is overflowed from the top of the water washing tower, and the catalyst carrying the reaction water is recovered from the bottom. The catalyst carrying the reaction water is continuously returned to the jet loop reactor for continuous catalytic reaction. The continuous reaction is carried out for 72 hours, and the crude carboxylic acid 1753 kg is collected. After rectification, the neodecanoic acid 1726 kg is obtained, and the yield is 98.3%.

[0103] Example 6

[0104] In this example, the catalyst is BF3·2H2O (molecular weight 103.84, density 1636 kg / m 3 ), the olefin is dimerized isobutene (molecular weight 112.22, density 715 kg / m 3 ), and the product is neononanoic acid (molecular weight 158.26, density 895 kg / m 3); catalyst: olefin: catalyst carrying reaction water: water scrubbing tower washing water = 1.25:1:1:1 (molar ratio); the circulating pump flow rate was 1.2 m 3 / h, the head was 0.5 Mpa, the first stage nozzle liquid line speed was 27 m / s; the nozzle suction CO flow rate was 1.3 m 3 / h, the CO and olefin molar ratio was 6.9:1; the annular gap gas content was about 10%; the reaction pressure was 2 Mpa, the reaction temperature was 40°C, and the reaction retention time was 0.5 hours.

[0105] ①Initial reaction (start-up)

[0106] The catalyst 9.60 kg and the carrying reaction water 1.33 kg were added into the jet loop reactor, CO was used to replace the gas phase, and the pressure was increased to 2 Mpa, and during the reaction, CO was continuously introduced to maintain the pressure stable during the reaction. The circulating pump was started, and the circulating pump liquid flow rate was 1.2 m 3 / h, wherein the flow rate of the reaction liquid drawn from the bottom of the reactor was 1176.8 l / h, and the flow rate of the olefin added into the circulating reaction liquid by the metering pump was 23.2 l / h. The circulating reaction liquid and the added olefin were mixed on the circulating loop and heat-exchanged by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor was 40°C. The olefin and CO and the reaction water were reacted in the nozzle and the loop reactor under the action of the catalyst for 0.5 hours.

[0107] ②Continuous reaction

[0108] After the intermittent reaction was completed, the continuous feeding was started. The circulating pump flow rate was 1.2 m 3 / h, wherein the circulating flow rate of the reaction liquid drawn from the bottom of the reactor was 1162.4 l / h, the olefin was added into the reaction liquid circulating flow by the metering pump at 23.22 l / h, and the water-carrying catalyst was added at 14.4 / h (wherein the catalyst was 11.7 l / h, and the carrying reaction water was 2.7 l / h). When the reaction material height exceeded the set liquid level height, which was 550 mm in this example, the catalyst and the neodecanoic acid mixture was discharged from the bottom of the reactor to keep the liquid level constant at the set height. It re-entered the lower part of the water scrubbing tower for countercurrent extraction washing, the reaction water entered the water scrubbing tower from the bottom at 2.7 l / h, the crude carboxylic acid overflowed from the top of the water scrubbing tower, and the catalyst carrying the reaction water was recovered from the bottom. The water-carrying catalyst continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, and the crude carboxylic acid 1695 kg was collected, and the neononanoic acid 1670 kg was obtained by rectification, with a yield of 98.4%.

[0109] Example 7

[0110] In this example: the catalyst is BF3 / H2SO4 / H2O (molecular weight 183.8, density 1720 kg / m 3 ), the olefin is propylene (molecular weight 42.08, density 590 kg / m 3 ), and the product is acrolein (molecular weight 56.06, density 1040 kg / m 3 ); catalyst: olefin: catalyst-carrying reaction water: water washing tower washing water = 1.25: 1: 1: 1 (molar ratio); the circulating pump flow rate is 1.2 m 3 / h, the head is 0.5 Mpa, the first stage nozzle liquid line speed is 27 m / s; the nozzle suction CO flow rate is 1.3 m 3 / h, the CO and olefin molar ratio is 8.7:1; the annular gap gas content is about 10%; the reaction pressure is 2 Mpa, the reaction temperature is 40℃, and the reaction retention time is 0.5 hours.

[0111] ① Initial reaction (start-up)

[0112] The catalyst 13.4 kg and the reaction water 1.05 kg were added to the jet loop reactor, the gas phase was replaced with CO, and the pressure was increased to 2 Mpa. During the reaction, CO was continuously introduced to maintain the pressure stable during the reaction. The circulating pump was started, and the circulating pump liquid flow rate was 1.2 m 3 / h, including the flow rate of the reaction liquid drawn from the bottom of the reactor was 1180.1 l / h, and the flow rate of the olefin added to the circulating reaction liquid by the metering pump was 19.9 l / h. The circulating reaction liquid and the added olefin were mixed on the circulating loop and heat exchanged by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor was 40℃. The olefin and CO and the reaction water reacted under the action of the catalyst in the nozzle and the loop reactor for 0.5 hours.

[0113] ② Continuous reaction

[0114] After the intermittent reaction was completed, continuous feeding was started. The circulating pump flow rate was 1.2 m 3The reactor operates at a rate of 1162.4 L / h for the circulating reaction liquid drawn from the bottom. Olefins are added to the circulating reaction liquid at a rate of 19.9 L / h via metering pumps, and water-carrying catalyst (15.6 L / h catalyst and 2.1 L / h water-carrying catalyst) is added at a rate of 17.7 L / h. When the reactant height exceeds 550 mm, the mixture of catalyst and neodecanoic acid is discharged from the bottom of the reactor to maintain a constant liquid level of 550 mm. This discharged mixture then undergoes countercurrent extraction and washing in the lower part of a water washing tower. Reaction water enters the water washing tower from the bottom at a rate of 2.1 L / h, and crude carboxylic acid overflows from the top of the tower. The catalyst carrying the reaction water is recovered from the bottom. This water-carrying catalyst is continuously returned to the jet circulating reactor to continue the catalytic reaction. After 72 hours of continuous reaction, 1458 kg of crude carboxylic acid is collected, and 1439 kg of neodecanoic acid is obtained by distillation, with a yield of 98.6%.

[0115] Example 8

[0116] In this embodiment: the catalyst is BF3·2H2O (molecular weight 103.84, density 1636 kg / m³). 3 The olefin is tripropylene (molecular weight 126, density 740 kg / m³). 3 The product is neodecanoic acid (molecular weight 172.26, density 910 kg / m³). 3 The molar ratio of catalyst: olefin: catalyst-carrying reaction water: water washing tower wash water is 1:1:1:1 (molar ratio); the circulation pump flow rate is 1.3 m³ / s. 3 The flow rate is 1.5 m³ / h, the head is 0.5 MPa, the liquid linear velocity of the first-stage nozzle is 29 m / s; the CO flow rate drawn in by the nozzle is 1.5 m³ / h, the molar ratio of CO to olefins is 5.2:1; the annular gas holdup is about 11%; the reaction pressure is 1 MPa, the reaction temperature is 60 °C, and the reaction retention time is 0.7 hours.

[0117] ① Initial reaction (driving)

[0118] 7.67 kg of catalyst and 1.33 kg of reaction water were added to the jet circulation reactor. The gas phase was replaced with CO, and the pressure was increased to 1 MPa. During the reaction, CO was continuously introduced to maintain a stable pressure. The circulation pump was started, with a liquid flow rate of 1.3 m³ / h. 3 The flow rate includes 1282 l / h of reaction liquid extracted from the bottom of the reactor and 18 l / h of olefins added to the circulating reaction liquid via a metering pump. The circulating reaction liquid and the added olefins are mixed in the circulation loop and heat exchanged through a heat exchanger to maintain the liquid temperature entering the reaction nozzle and circulating reactor at 60°C. The olefins, CO, and reaction water react in the nozzle and circulating reactor under the action of a catalyst for 0.7 hours.

[0119] ② Continuous reaction

[0120] After the initial reaction, continuous feeding was started. The circulation pump flow rate was 1.3 m 3 / h, in which the circulation flow rate of the reaction liquid taken from the bottom of the reactor was 1273 l / h, the olefin was added to the reaction liquid circulation flow at a rate of 18 l / h by means of a metering pump, and the catalyst carrying reaction water was added at a rate of 8.6 / h (in which the catalyst was 6.7 l / h and the reaction water was 1.9 l / h). When the reaction material height exceeded 550 mm, the catalyst and neodecanoic acid mixture was discharged from the bottom of the reactor to maintain the liquid level at 550 mm. The mixture was then introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water was introduced into the water washing tower from the bottom at a rate of 1.9 l / h, the crude carboxylic acid overflowed from the top of the water washing tower, and the catalyst carrying reaction water was recovered from the bottom. The catalyst carrying water was continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, 1320 kg of crude carboxylic acid was collected, 1304 kg of neodecanoic acid was obtained by rectification, and the yield was 98.6%.

[0121] Example 9

[0122] In this example: the catalyst was BF3·2H2O (molecular weight 103.84, density 1636 kg / m 3 ), the olefin was tetrapropylene (molecular weight 168, density 776 kg / m 3 ), and the product was neodecanoic acid (molecular weight 214.26, density 930 kg / m 3 ); the catalyst: olefin: catalyst carrying reaction water: water washing tower washing water = 1:1:1:1 (molar ratio); the circulation pump flow rate was 1.3 m 3 / h, the head was 0.5 Mpa, and the liquid line speed of the first stage nozzle was 29 m / s; the CO flow rate sucked by the nozzle was 1.5 m 3 / h, and the CO and olefin molar ratio was 6.2:1; the annular gap gas content was about 11%; the reaction pressure was 1 Mpa, the reaction temperature was 60℃, and the reaction residence time was 0.7 hours.

[0123] ① Initial reaction (start-up)

[0124] The catalyst 6.48 kg and the reaction water carrying 1.12 kg were added to the jet loop reactor, CO was used to replace the gas phase, and the pressure was increased to 1 Mpa, and CO was continuously introduced during the reaction to maintain the pressure stable during the reaction. The circulation pump was started, and the liquid flow rate of the circulation pump was 1.3 m 3= 1.3 m3 / h, the flow rate of the reaction liquid drawn from the bottom of the reactor = 1280.7 l / h, and the flow rate of the olefin added to the circulating reaction liquid by the metering pump = 19.3 l / h. The circulating reaction liquid and the added olefin are mixed on the circulating loop and are heat-exchanged by the heat exchanger, so that the temperature of the liquid entering the reaction nozzle and the loop reactor is 60°C. The olefin and CO and the reaction water are reacted in the presence of the catalyst in the nozzle and the loop reactor for 0.7 hours.

[0125] ② Continuous reaction

[0126] After the batch reaction is completed, continuous feeding is started. The circulating pump flow rate = 1.3 m 3 / h, the circulating flow rate of the reaction liquid drawn from the bottom of the reactor = 1273.4 l / h, the olefin is added to the circulating flow of the reaction liquid by the metering pump at 19.3 l / h, and the catalyst carrying the reaction water is added at 7.3 l / h (of which the catalyst = 5.7 l / h and the reaction water = 1.6 l / h). When the reaction material height exceeds 550 mm, the catalyst and the neodecanoic acid are discharged from the bottom of the reactor to maintain the liquid level constant at 550 mm. This is then introduced into the lower part of the water scrubbing column for countercurrent extraction washing, the reaction water is introduced into the water scrubbing column from the bottom at 1.6 l / h, the crude carboxylic acid overflows from the top of the water scrubbing column, and the catalyst carrying the reaction water is recovered from the bottom. This catalyst carrying the reaction water is continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction is carried out for 72 hours, 1387 kg of crude carboxylic acid is collected, and 1369 kg of neodecanoic acid is obtained by rectification, with a yield of 98.7%.

[0127] Example 10

[0128] In this example: the catalyst is BF3 / 0.7 H3PO4 / 0.7 H2O (molecular weight = 149, density = 1750 kg / m 3 ), the olefin is propylene (molecular weight = 42.08, density = 590 kg / m 3 ), and the product is neopentanoic acid (molecular weight = 86.12, density = 860 kg / m 3 ); the catalyst: olefin: catalyst carrying the reaction water: water scrubbing column washing water = 1:1:1:1 (molar ratio); the circulating pump flow rate = 1.3 m 3 / h, the head = 0.5 Mpa, and the liquid line velocity of the first stage nozzle = 29 m / s; the flow rate of CO drawn into the nozzle = 1.5 m 3 / h, the molar ratio of CO to olefin = 5.7:1; the annular gap gas content = about 11%; the reaction pressure = 1 Mpa, the reaction temperature = 60°C, and the reaction residence time = 0.7 hours.

[0129] ① Initial reaction (start-up)

[0130] The catalyst 10.14 kg and the reaction water 1.22 kg were added into the jet loop reactor, the gas phase was replaced by CO, and the pressure was increased to 1 MPa, and the pressure was kept stable during the reaction by continuously feeding CO. The circulating pump was started, and the circulating pump liquid flow rate was 1.3 m 3 / h, including the flow rate of the reaction liquid taken out from the bottom of the reactor was 1283.5 l / h, and the flow rate of the olefin added into the circulating reaction liquid by the metering pump was 16.5 l / h. The circulating reaction liquid and the added olefin were mixed on the circulating loop and were heat-exchanged by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor was 60°C. The olefin and CO and the reaction water reacted in the presence of the catalyst in the nozzle and the loop reactor for 0.7 hours.

[0131] 2. Continuous reaction

[0132] After the end of the batch reaction, the continuous feeding was started. The circulating pump flow rate was 1.3 m 3 / h, including the circulating flow rate of the reaction liquid taken out from the bottom of the reactor was 1273.4 l / h, the olefin was added into the circulating flow of the reaction liquid by the metering pump at a flow rate of 16.6 l / h, and the catalyst carrying reaction water was added at a flow rate of 10 l / h (including the catalyst 8.3 l / h and the reaction water 1.7 l / h). When the reactant material height exceeded 550 mm, the material was discharged from the bottom of the reactor to keep the liquid level constant at 550 mm, and the material was a mixture of the catalyst and the neodecanoic acid. The material was introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water was introduced into the water washing tower from the bottom at a flow rate of 1.7 l / h, the crude carboxylic acid overflowed from the top of the water washing tower, and the catalyst carrying reaction water was recovered from the bottom. The catalyst carrying reaction water was continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, 1215 kg of crude carboxylic acid was collected, 1196 kg of neodecanoic acid was obtained by rectification, and the yield of neodecanoic acid was 98.3%.

[0133] Example 11

[0134] In this example: the catalyst was BF3·2H2O (molecular weight was 103.84, density was 1636 kg / m 3 ), the olefin was tripropylene (molecular weight was 126, density was 740 kg / m 3 ), and the product was neodecanoic acid (molecular weight was 172.26, density was 910 kg / m 3 ); the catalyst: olefin: catalyst carrying reaction water: washing water of the water washing tower = 0.7:1:1:1 (molar ratio); the circulating pump flow rate was 1.4 m 3 / h, the head was 0.5 MPa, and the liquid line velocity of the first stage nozzle was 31 m / s; the CO flow rate sucked by the nozzle was 1.6 m 3The molar ratio of H2, CO and olefin is 3.6:1; the gas holdup is about 13%; the reaction pressure is 0.5 MPa, the reaction temperature is 80°C, and the reaction retention time is 1 hour.

[0135] ① Initial reaction (start-up)

[0136] The catalyst 5.68 kg and the reaction water 1.41 kg are added into the jet loop reactor, the gas phase is replaced by CO, and the pressure is increased to 0.5 MPa, and during the reaction, CO is continuously introduced to maintain the pressure stable during the reaction. The circulation pump is started, the circulation pump liquid flow is 1.4 m 3 / h, and the olefin is added into the circulation reaction liquid by the metering pump at a flow rate of 13.3 l / h. The circulation reaction liquid and the added olefin are mixed on the circulation loop and are heated by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor is 80°C. The olefin and CO and the reaction water are reacted in the presence of the catalyst in the nozzle and the loop reactor for 1 hour.

[0137] ② Continuous reaction

[0138] After the batch reaction is finished, the continuous feeding is started. The circulation pump flow is 1.4 m 3 / h, the circulation flow of the reaction liquid from the bottom of the reactor is 1381.8 l / h, the olefin is added into the circulation flow of the reaction liquid by the metering pump at a flow rate of 13.3 l / h, and the catalyst with reaction water is added at a flow rate of 4.9 l / h (of which the catalyst is 3.5 l / h, and the reaction water is 1.4 l / h). When the reaction material height exceeds 550 mm, the material is discharged from the bottom of the reactor to keep the liquid level constant at 550 mm, and the discharged material is the mixture of the catalyst and the neodecanoic acid. The mixture is introduced into the lower part of the water washing tower for countercurrent extraction washing, the reaction water is introduced into the water washing tower from the bottom at a flow rate of 1.7 l / h, the crude carboxylic acid is overflowed from the top of the water washing tower, and the catalyst with reaction water is recovered from the bottom. The catalyst with reaction water is continuously returned to the jet loop reactor for continuous catalytic reaction. The continuous reaction is carried out for 72 hours, and the crude carboxylic acid 980 kg is collected. The neodecanoic acid is obtained by rectification at a yield of 97.4%.

[0139] Example 12

[0140] In this example: the catalyst is BF3·2H2O (molecular weight is 103.84, density is 1636 kg / m 3 ), the olefin is tripropylene (molecular weight is 126, density is 740 kg / m 3 ), and the product is neodecanoic acid (molecular weight is 172.26, density is 910 kg / m 3); catalyst: olefin: catalyst carrying reaction water: water scrubbing tower washing water = 0.5:1:1:1 (molar ratio); the circulating pump flow rate was 1.5 m 3 / h, the head was 0.5 Mpa, the liquid line velocity of the first stage nozzle was 33 m / s; the CO flow rate sucked by the nozzle was 1.78 m 3 / h, the CO and olefin molar ratio was 7.2:1; the annular gap gas content was about 15%; the reaction pressure was 0.1 Mpa, the reaction temperature was 100°C, and the reaction retention time was 10 hours.

[0141] ① Initial reaction (start-up)

[0142] The catalyst 4.19 kg and the carrying reaction water 1.45 kg were added into the jet loop reactor, CO was used to replace the gas phase, and the pressure was increased to 0.1 Mpa, and during the reaction, CO was continuously introduced to maintain the pressure stable during the reaction. The circulating pump was started, and the circulating pump liquid flow rate was 1.5 m 3 / h, wherein the flow rate of the reaction liquid drawn from the bottom of the reactor was 1498.6 l / h, and the flow rate of the olefin added into the circulating reaction liquid by the metering pump was 1.4 l / h. The circulating reaction liquid and the added olefin were mixed on the circulating loop and heat exchanged by the heat exchanger, so that the liquid temperature entering the reaction nozzle and the loop reactor was 100°C. The olefin and CO and the reaction water reacted under the action of the catalyst in the nozzle and the loop reactor for 10 hours.

[0143] ② Continuous reaction

[0144] After the intermittent reaction was completed, continuous feeding was started. The circulating pump flow rate was 1.5 m 3 / h, wherein the circulating flow rate of the reaction liquid drawn from the bottom of the reactor was 1498.2 l / h, the olefin was added into the reaction liquid circulating flow by the metering pump at 1.4 l / h, and the water-carrying catalyst was added at 0.4 l / h (wherein the catalyst was 0.26 l / h, and the reaction water was 0.15 l / h). When the reaction material height exceeded 550 mm, the catalyst and the neodecanoic acid mixture was discharged from the bottom of the reactor to maintain the liquid level constant at 550 mm. It re-entered the lower part of the water scrubbing tower for countercurrent extraction washing, the reaction water entered the water scrubbing tower from the bottom at 0.15 l / h, the crude carboxylic acid overflowed from the top of the water scrubbing tower, and the catalyst carrying the reaction water was recovered from the bottom. The water-carrying catalyst continuously returned to the jet loop reactor to continue the catalytic reaction. The continuous reaction was carried out for 72 hours, and 114 kg of crude carboxylic acid was collected, 111 kg of neodecanoic acid was obtained by rectification, and the yield was 97.3%.

[0145] Compared with the pressurized reaction kettle in the prior art, the mechanical stirring also has problems of high electric power and poor mass transfer effect, the expensive stirring device needs to be pressure-resistant and leakage-resistant, and the cooling coil is easy to be corroded and limited in heat exchange area; while the jet loop reactor of the application does not need to set dynamic seal and mechanical stirring structure, the external heat exchanger can fully meet the process requirements in heat exchange area and heat transfer coefficient, the circulating pump has low power, and the mass transfer effect is good by virtue of the efficient design of the nozzle and the loop reactor, the reaction retention time is sufficient, and these advantages jointly ensure the production of carboxylic acid under mild conditions at low cost and high yield.

[0146] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or replace the preparation reaction conditions, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A process for producing an aliphatic carboxylic acid, characterized by, The method comprises the following steps: (a) adding liquid inorganic acid catalyst carrying reaction water into a downward liquid jet loop reactor, wherein the amount of reaction water is at least sufficient to react with olefins to be reacted in stoichiometric amount; introducing carbon monoxide gas into the upper part of the reactor, and the partial pressure of the carbon monoxide gas is 0.1-10 MPa; (b) establishing a circulation loop: using a circulating pump to extract the solution in the reactor, and after temperature control by a heat exchanger, delivering the solution to the two-stage jet nozzle at the top of the reactor; (c) using a metering pump to add olefins to the circulation loop in step (b); (d) the mixture in the circulation loop is sprayed out through the first-stage nozzle, and the negative pressure generated automatically sucks the carbon monoxide gas in the reactor into the second-stage nozzle, and the gas-liquid two-phase mixture in the second-stage nozzle is mixed and reacted to generate aliphatic carboxylic acid; (e) the material flows downward into the draft tube of the reactor, turns after impacting the draft plate below, and flows upward along the annular gap between the draft tube and the inner wall of the reactor to form a loop for sufficient reaction; (f) discharging the reaction product, separating and purifying to obtain the aliphatic carboxylic acid product, and recycling the recovered catalyst solution; The device for the above method comprises: a reaction unit comprising a downward liquid jet loop reactor, wherein a hollow cylindrical draft tube and a draft plate are arranged inside the reactor, a first-stage nozzle and a second-stage nozzle are arranged from top to bottom at the top of the reactor to form a two-stage jet nozzle, a carbon monoxide gas inlet is arranged between the first-stage nozzle and the second-stage nozzle, an annular channel is formed between the outer wall of the draft tube and the inner wall of the reactor body, the spraying direction of the second-stage nozzle is toward the space inside the draft tube, and the draft plate is located directly below the draft tube and is configured to change the flow direction of the intercepted material from vertical downward to the annular channel; a catalyst circulation unit comprising a circulating pump, a heat exchanger and a material circulation pipeline, wherein the inlet of the circulating pump is communicated with the reaction product outlet at the bottom of the reactor, and the material circulation pipeline is provided with a heat exchanger and connected to the first-stage nozzle; an olefin feeding unit comprising an olefin feeding pipeline and a metering pump, wherein the olefin feeding pipeline is connected to the material circulation pipeline between the outlet of the circulating pump and the inlet of the heat exchanger in the catalyst circulation unit; a carbon monoxide feeding unit communicated with the upper part of the reactor; a separation and purification unit comprising a water washing tower, wherein the material inlet at the bottom of the water washing tower is connected with the reaction product outlet of the reactor, and the catalyst solution outlet at the bottom is connected with the catalyst circulation unit.

2. The method of claim 1, wherein, The liquid flow rate of the first-stage nozzle is 15-35 m / s, and the annular gap gas holdup between the inner wall of the reactor and the draft tube is 8%-15%.

3. The method of claim 2, wherein, The liquid flow rate is 24-30 m / s, and the annular gap gas holdup is 9-11%.

4. The method of claim 3, wherein, The molar ratio of reaction water to olefins is 1-1.15:1, and the molar ratio of the amount of carbon monoxide introduced into the reactor to the theoretical consumption of carbon monoxide in the reaction is greater than 3:

1.

5. The method of claim 1, wherein, The inorganic acid catalyst is sulfuric acid, boron trifluoride or a composite of boron trifluoride and sulfuric acid / phosphoric acid.

6. The method of claim 1, wherein, The inorganic acid catalyst comprises at least boron trifluoride or boron trifluoride dihydrate, wherein the molar ratio of boron trifluoride to olefin is 0.5-5:

1.

7. The method of claim 1, wherein, The olefin is isobutene, dimeric isobutene, or C6 to C 15 propylene oligomers.

8. The method according to any one of claims 1 to 7, characterized in that, The control temperature is 0-100℃, and the reaction time is 0.1-10 hours.

9. The method of claim 8, wherein, The control temperature is 30-60℃, the partial pressure of carbon monoxide gas is 1-5Mpa, and the reaction time is 0.2-1 hour.

10. The method of claim 1, wherein, The olefin is a C2-C 24 Olefin.

11. The method of claim 1, wherein, The aliphatic carboxylic acid is a tertiary carbonic acid.

12. An apparatus for use in the process for producing an aliphatic carboxylic acid according to any one of claims 1 to 11, characterized by, It comprises: A reaction unit comprising a downward spraying liquid jet loop reactor, the reactor is internally provided with a hollow cylindrical draft tube and a draft plate, the top of which is arranged with a first stage nozzle and a second stage nozzle from top to bottom, forming a two-stage jet nozzle; a carbon monoxide gas inlet is arranged between the first stage nozzle and the second stage nozzle; an annular gap channel is formed between the outer wall of the draft tube and the inner wall of the reactor body, and the jet direction of the second stage nozzle is towards the inner space of the draft tube; the draft plate is located directly below the draft tube and is configured to change the flow direction of the intercepted material from vertical downward to the annular gap channel; A catalyst circulation unit comprising a circulation pump, a heat exchanger and a material circulation pipeline, the inlet of the circulation pump is in communication with the reaction product outlet at the bottom of the reactor, and the heat exchanger is arranged on the material circulation pipeline and connected to the first stage nozzle; An olefin feed unit comprising an olefin feed pipeline and a metering pump, the olefin feed pipeline is connected to the material circulation pipeline in the catalyst circulation unit between the outlet of the circulation pump and the inlet of the heat exchanger; A carbon monoxide feed unit in communication with the upper part of the reactor; A separation and purification unit comprising a water washing tower, the material inlet at the bottom of which is connected to the reaction product outlet of the reactor; the catalyst solution outlet at the bottom is connected to the catalyst circulation unit.

13. The apparatus of claim 12, wherein, The separation and purification unit further comprises a recovery tower and a desolvation tower, the recovery catalyst solution outlet of the water washing tower is connected to the catalyst circulation unit and the recovery tower for concentrating catalyst solution respectively, the concentrated catalyst solution outlet of the recovery tower is connected to the catalyst circulation unit, and the water removal outlet is connected to the water washing tower.

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