CN111470962A - A kind of method for preparing isononanoic acid by mixed isomeric octene - Google Patents

Abstract

The invention discloses a method for preparing isononanoic acid by hydroformylation and oxidation of mixed iso-octene in two steps. In the presence of a novel porous organic polymer-supported metal rhodium (Rh)-based catalyst, mixed iso-octene was hydroformylated to obtain isononanal, which was then oxidized with oxygen-containing gas at low temperature in an oxidation reactor. , Under low pressure and no catalyst, the oxidation reaction occurs to generate isononanoic acid. The invention can realize the efficient and highly selective conversion of mixed isomerized octene into the target product isononanoic acid under mild reaction conditions, and the product and the reaction material can be easily separated, and the obtained target product has a high single-pass yield.

Description

A kind of method for preparing isononanoic acid by mixed isomeric octene

technical field

The invention relates to the technical field of chemical catalysis, in particular to a method for preparing isononanoic acid from mixed isomerized octene.

Background technique

Isononanoic acid (3,5,5-trimethylhexanoic acid) is a very important organic raw material, which can be used to synthesize fragrances, pharmaceutical intermediates, lubricating oils, raw materials for metal working fluids, etc. At the same time, it can also react with various alcohol compounds to form various isononanoate esters. For example, vinyl isononanoate, glycidyl ester, carboxylate, isononanoyl halide, isononanoic anhydride and isononanoamide, and the like. Among them, isononanoate can be synthesized by esterification of isononanoic acid and isononanol in the presence of p-toluenesulfonic acid, sulfamic acid, or sodium bisulfate as a catalyst (CN102503819A). It is a light oil and an excellent emollient, commonly known as "silk oil", it can form a hydrophobic film on the skin surface, making the skin shiny, smooth and non-greasy, so it is an ideal cosmetic Use grease.

Isononanoic acid is mainly obtained by oxidation production process. The raw material can be isononanal (3,5,5-trimethylhexanal), and the mixed iso-octene is converted into isononanal by olefin hydroformylation process, and then isonononal is oxidized to obtain isononanoic acid (CN108047027A ); it can also be 2-ethylhexanol, octene is generated by dehydration of 2-ethylhexanol, and then octene is hydroformylated to generate isononanal, which is then oxidized to generate isononanoic acid (CN104379543A). In addition, the water-soluble palladium phosphine complex catalyst system can also directly generate nonanoic acid and isononanoic acid through the carbonylation reaction of octene (CN102040501A), but this method needs to add a phase transfer agent or an acid auxiliary, and the target product is nonononanoic acid. Acid-based.

Most of the industrial production routes of isononanal use the hydroformylation method. This reaction process has been systematically studied at home and abroad (US Pat. 4528403; CN104395264A; CN1587244A), and unique proprietary catalyst technologies have been developed, including: carbonyl cobalt catalytic system, phosphine ligand modified cobalt catalytic system, Phosphine ligand-modified rhodium catalytic system, etc. At present, the industrial production technology for preparing isononanal by the hydroformylation of mixed isomerized octene mainly uses a homogeneous catalyst system, which is not conducive to the recycling of the catalyst. Compared with the homogeneous catalyst, the heterogeneous catalyst is easier to separate from the reaction material. However, the activity is lower under the same reaction conditions. Therefore, the development of catalysts with high activity and selectivity for homogeneous reactions and easy separation and stability for heterogeneous reactions has become the main goal of research in this field.

In the process of oxidizing isonanoic acid to isonanoic acid, transition metals or transition metal compounds such as titanium, vanadium, chromium, molybdenum, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium or copper can be used as catalysts (US2015 /0191410A1), single compounds such as lithium isononanoate, potassium isononanoate, sodium isononanoate, calcium isononanoate or barium isononanoate, etc. can also be used as catalysts. However, the above processes may lead to the accumulation of metal ions in the reaction solution, the increase of by-products, and the decrease of the selectivity of isononanoic acid. Therefore, developing a simple and efficient process for preparing isononanoic acid has become a difficulty in the prior art.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a kind of method for preparing isononanoic acid from mixed isomerized octene, in particular to use mixed isomerized octene as raw material to synthesize isononanal through hydroformylation reaction, and then isonononal is oxidized in an oxidation reactor. Method for the synthesis of isononanoic acid in . The present invention solves the problems in the prior art such as low yield and selectivity of isononanoic acid.

The present invention adopts following technical scheme:

A method for preparing isononanoic acid from mixed isomerized octene, wherein the mixed isomerized octene undergoes a hydroformylation reaction under the action of a Rh-based catalyst supported by a porous organic polymer to generate isonononal, and then the isonononal is oxidized Oxidation reaction occurs with oxygen-containing gas in the reactor under low temperature, low pressure and catalyst-free conditions to generate isononanoic acid;

The specific process of the hydroformylation reaction is as follows: using a high-pressure pump to drive the liquid mixed isomerized octene into the reactor, and at a certain pressure and temperature, perform a hydroformylation reaction with synthesis gas in the presence of a catalyst to obtain isononyl. Aldehydes; the mixed iso-octene consists of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl- ₂ -pentene, the syngas is CO and H The catalyst is a highly dispersed heterogeneous solid catalyst composed of a main active component and a carrier, the main active component is Rh, and the carrier is a porous organic polymer, that is, a porous organic polymer-supported Rh-based catalyst ; The porous organic polymer is a polymer with rich hierarchical pore structure and large specific surface area, which is formed by the modification of organic ligands containing P and optional N or S functional elements through vinyl functional groups and then polymerized; The mass fraction of the main active components is 0.01% to 20%, and the rest are carriers;

The oxidation reactor includes a reactor body, a flow controller, a bubble distributor, a stirrer, a back pressure valve, and a heat exchanger. The reactor body is provided with an inlet/outlet; the bubble distributor is arranged in the lower part of the reactor body , the stirring blade of the agitator is arranged at the lower part of the bubble distributor in the reactor body; the outlet of the oxygen-containing gas storage tank is provided with a pressure reducing valve and a pressure gauge, and the oxygen-containing gas storage tank is connected with the inlet of the flow controller through the first pipeline. The first pipeline is provided with a shut-off valve, the outlet of the flow controller is connected with the bubble distributor through the second pipeline; the back pressure valve is connected with the reactor body through the third pipeline, and the third pipeline is provided with a pressure gauge; the heat exchanger is located in The outer periphery and bottom of the reactor body;

The specific process of the oxidation reaction is as follows:

Step 1), a certain amount of isononanal is added into the oxidation reactor body through the liquid inlet/outlet, and the gas in the oxidation reactor is replaced with an inert gas;

Step 2), heating the oxidation reactor body by the heat exchanger, so that the temperature in the oxidation reactor body is raised to a specified value;

Step 3), the agitator is turned on;

Step 4), the oxygen-containing gas controls the flow rate and flow rate through the flow controller, and is passed into the isononanal reaction solution by bubbling through the bubble distributor, so that it is evenly distributed in the isononanal reaction solution; through the back pressure The valve regulates the pressure in the oxidation reactor body;

Step 5) After a certain time of reaction, stop stirring and oxygen supply, and take out the reaction product from the liquid inlet/outlet.

Further, the organic ligand containing P and optional N or S functional elements is composed of one or more of the following ligands:

Further, the Rh-based catalyst immobilized on the porous organic polymer is prepared by an impregnation method or/and an ultrasonic method.

Further, the molar ratio of CO and H ₂ in the syngas is 1:10-100:1.

Further, in the hydroformylation reaction, the reaction pressure is 0.1-30 MPa, the reaction temperature is 50-200° C., the weight hourly space velocity of the mixed isomerized octene is 0.01-20 h ^-1 , and the gas space velocity of the synthesis gas is 1-10000 h ^-1 .

Further, the reactor in the hydroformylation reaction is a fixed bed reactor or a slurry bed reactor.

Further, the device used for preparing isononanal by mixing isomerized octene includes: a high-pressure pump for pumping liquid mixed isooctene; a mixer for mixing the synthesis gas and the mixed isooctene reaction material; a reactor for mixing with the mixed isooctene. The outlet of the mixer is connected and filled with a porous organic polymer-supported Rh-based catalyst to realize the heterogeneous catalytic reaction of the carbonylation of mixed isooctene; a product collection tank is used to collect the reaction product obtained from the reactor ; On-line gas chromatography for analysis of tail gas and liquid products.

Further, the oxygen-containing gas is O ₂ /N ₂ , O ₂ /He, O ₂ /Ar or pure oxygen, and the O ₂ concentration is 10-100 v/v%.

Further, in the oxidation reaction, isononanal is measured at 5-20 mL, the flow rate of the oxygen-containing gas is 5-100 mL/min, and the reaction is carried out at 20-100° C., 1-25 atm, and catalyst-free for 1-20 h.

Beneficial effects of the present invention:

1. The isononanal of the present invention is obtained by the hydroformylation reaction of mixed isomerized octene, which can be realized under relatively low pressure and temperature reaction conditions; a novel porous organic polymer is used to immobilize rhodium (Rh) based highly dispersed heterogeneous phase The solid catalyst has high selectivity, excellent stability, and easy separation of the catalyst and the reaction material; the use of a fixed bed reactor has a simple reaction process and convenient operation, reduces the one-time investment and production cost of production and subsequent separation devices, and is easy to implement Large-scale continuous industrial production.

2. If the oxidation reaction is carried out under relatively harsh conditions, such as high temperature, high pressure, high-speed oxygen, etc., on the one hand, it may accelerate the formation rate of peroxides, and thus accumulate in the reactor and increase the formation of by-products On the other hand, it may also lead to a violent exothermic reaction, the yield of the target acid will decrease, and the safety hazard will be increased. Therefore, controlling the reaction conditions to convert isononanoal to isononanoic acid at a suitable rate is crucial for the reaction. The present invention is conditioned by a specific oxidation reactor. The oxygen-containing gas is contacted with the liquid reaction raw material isononanal through the flow controller and the bubble distributor. The flow controller can control the gas flow rate, adjust the oxygen-containing gas of one of the reaction raw materials and then adjust the reaction speed; the bubble distributor controls the feeding reaction The size of the bubbles in the gas-liquid oxidation reaction is the specific surface size of the bubbles, so the oxidation reaction rate can be controlled by controlling the size of the bubbles; in addition, the gas-liquid contact surface can be assisted by the agitator to adjust the reaction rate; The valve can control the internal pressure of the reactor, and then control the progress of the oxidation reaction by controlling the internal pressure of the reactor. The present invention realizes that the isononanal can be efficiently and selectively converted into the target product isononanoic acid under mild reaction conditions (low temperature, low pressure, and no catalyst).

Description of drawings

Fig. 1 is a schematic diagram of the device structure used for preparing isononanal by mixing isomerized octene;

Globe Valve 1, Pressure Gauge 2, Purification Tank 3, Globe Valve 4, Pressure Regulating Valve 5, Globe Valve 6, Filter 7, Mass Flow Meter 8, Check Valve 9, Mixer 10, Globe Valve 11, High Pressure Pump 12 , filter 13, shut-off valve 14, reactor 15, shut-off valve 16, product collection tank 17, shut-off valve 18, back pressure valve 19, shut-off valve 20, shut-off valve 21, rotameter 22, online gas chromatography 23.

Fig. 2 is the oxidation reactor structure schematic diagram that isononanal is oxidized to generate isononanoic acid;

Reactor body 101 , flow controller 102 , bubble distributor 103 , agitator 104 , back pressure valve 105 , heat exchanger 106 , oxygen-containing gas storage tank 107 , pressure reducing valve 108 , shut-off valve 109 .

Detailed ways

The present invention will be further explained below with reference to the embodiments and the accompanying drawings. The following examples are only used to illustrate the present invention, but are not intended to limit the scope of implementation of the present invention.

A method for preparing isononanoic acid from mixed isomerized octene, wherein the mixed isomerized octene undergoes a hydroformylation reaction under the action of a Rh-based catalyst supported by a porous organic polymer to generate isonononal, and then the isonononal is oxidized In the reactor, the oxidation reaction occurs with oxygen-containing gas under the condition of low temperature, low pressure and no catalyst to generate isononanoic acid.

The specific process of the hydroformylation reaction is as follows:

The liquid mixed isomerized octene is pumped into the reactor by using a high pressure pump, and at a certain pressure and temperature, the hydroformylation reaction is carried out with the synthesis gas in the presence of a catalyst to obtain isononanal.

The mixed iso-octene consists of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene.

The synthesis gas is a mixed gas composed of CO and H ₂ , and the molar ratio of CO and H ₂ is 1:10～100:1, preferably 1:3～3:1; more preferably, 1:1.2～ 1.2:1.

The catalyst is a highly dispersed heterogeneous solid catalyst composed of a main active component and a carrier, the main active component is Rh, and the carrier is a porous organic polymer (POP), that is, a Rh-based catalyst immobilized by a porous organic polymer; The mass fraction of the active component is 0.01% to 20%, and the rest is the carrier; preferably, the mass fraction of the main active component is 0.1% to 2%, and the rest is the carrier. The porous organic polymer is a polymer with abundant hierarchical pore structure and large specific surface area, which is obtained by modifying organic ligands containing P and optional N or S functional elements through vinyl functional groups and then polymerizing.

The organic ligands containing P and optional N or S functional elements are composed of one or more of the following ligands:

The preparation of porous organic polymers can refer to patent CN104710288B. The porous organic polymer-supported Rh-based catalyst is prepared by impregnation method or/and ultrasonic method well known in the art.

Ultrasonic preparation can use the following steps:

(1) dissolving the rhodium precursor in an anhydrous ethanol reagent, and configuring a solution with a rhodium ion concentration of 0.0001 to 1 mol/L; the rhodium precursor is rhodium nitrate, rhodium phosphate, rhodium trichloride, rhodium acetylacetonate, rhodium carbonyl , one or more of phenyl rhodium, etc.;

(2) weigh a certain amount of porous organic polymer and add it to the solution obtained in step (1), and stir to obtain a mixed solution;

(3) the mixed solution obtained in step (2) is placed in a sonicator, and ultrasonically treated for 5～200min;

(4), filter the mixed solution after ultrasonic treatment in step (3), add ethanol washing, wash away the rhodium ion attached to the porous organic polymer surface, obtain the sample;

(5), treating the sample obtained in step (4) in a 353-473K vacuum drying oven for 1-48 hours, preferably 10-24 hours, to prepare a rhodium-based heterogeneous catalyst supported by a porous organic polymer.

The reaction pressure is 0.1～30MPa, the reaction temperature is 50～200℃, the weight hourly space velocity of the mixed isomerized octene is 0.01～20h ^-1 , and the gas space velocity of the synthesis gas is 1～10000h ^-1 ; preferably, the reaction pressure is 2～6MPa, the reaction temperature is 80～140℃, the weight hourly space velocity of mixed isomerized octene is 0.01～1.5h ^-1 , and the gas space velocity of synthesis gas is 300～3000h ^-1 .

The reactor is a fixed bed reactor or a slurry bed reactor, preferably, a fixed bed reactor.

As shown in Figure 1, the device used for preparing isononanal by mixing isomerized octene comprises: high-pressure pump 12, for pumping liquid mixed isooctene; mixer 10, realizing the mixing of synthesis gas and mixed isooctene reaction material; The reactor 15 is connected to the outlet of the mixer 10 and is filled with a porous organic polymer-supported Rh-based catalyst to realize the heterogeneous catalytic reaction of the carbonylation of mixed isooctene; the product collection tank 17 is used to collect from The reaction product obtained by the reactor 15; the online gas chromatography 23, for analyzing tail gas and liquid product, specifically using Agilent7890B for analysis, tail gas with PQ packed column, TCD detector; liquid product adopts HP-5 capillary chromatographic column, FID detector, with ethanol as internal standard for quantitative analysis.

Isononanoal is oxidized with oxygen-containing gas in the oxidation reactor under low temperature, low pressure, and without catalyst to form isononanoic acid, wherein the oxygen-containing gas is O ₂ /N ₂ , O ₂ /He, O ₂ /Ar Or pure oxygen, O ₂ concentration is 10~100v/v%; isononanal is calculated at 5~20mL, and the flow rate of oxygen-containing gas is 5~100mL/min, and the reaction is carried out at 20~100℃, 1~25atm, no catalyst. Carry out 1～20h.

The oxidation reactor includes a reactor body 101, a flow controller 102, a bubble distributor 103, an agitator 104, a back pressure valve 105, and a heat exchanger 106. The reactor body 101 is provided with an inlet/outlet (in FIG. 1 ). not shown); the bubble distributor 103 is arranged in the lower part of the reactor body 101, and the stirring blade of the agitator 104 is arranged in the lower part of the bubble distributor 103 in the reactor body 101; the outlet of the oxygen-containing gas storage tank 107 is provided with a pressure reducing valve 108 and pressure gauge, the oxygen-containing gas storage tank 107 is connected to the inlet of the flow controller 102 through the first pipeline, the first pipeline is provided with a stop valve 109, and the outlet of the flow controller 102 is connected to the bubble distributor 103 through the second pipeline; The pressure valve 105 is connected to the reactor body 101 through a third pipeline, and the third pipeline is provided with a pressure gauge; the heat exchanger 106 is arranged on the outer periphery and the bottom of the reactor body 101;

The specific process of the oxidation reaction is as follows:

Step 1), adding a certain amount of isononanal into the oxidation reactor body 101 through the liquid inlet/outlet, and replace the gas in the oxidation reactor with an inert gas;

Step 2), heating the oxidation reactor body 101 through the heat exchanger 106, so that the temperature in the oxidation reactor body 101 rises to a specified value;

Step 3), turn on the agitator 104;

Step 4), the oxygen-containing gas controls the flow rate and flow rate through the flow controller 102, and is passed into the isononanal reaction solution by bubbling through the bubble distributor 103, so that it is evenly distributed in the isononanal reaction solution; The back pressure valve 105 adjusts the pressure in the oxidation reactor body 101;

Step 5) After a certain time of reaction, stop stirring and oxygen supply, and take out the reaction product from the liquid inlet/outlet.

The preparation of the porous organic polymers involved in the following examples refers to examples 1-2 in patent CN104710288B. The preparation of the Rh-based catalyst immobilized on the porous organic polymer was prepared by the above-mentioned ultrasonic method.

Example 1

Weigh 1.0 g (about 1.5 mL) of the above-mentioned catalyst 5Rh/POP catalyst with a loading of 5‰ and put it into the constant temperature zone of the fixed-bed reactor. Firstly, syngas was introduced into the reaction system, and after purging for 10 min, the temperature was raised to 100 °C at a rate of 10 °C/min, and the pressure was increased to 3.0 MPa, waiting for the system to stabilize. Then the mixed octene is pumped into the mixer through a high-pressure pump, the weight hourly space velocity of the mixed octene is adjusted to be 0.02 g _{mixed octene} /g _catalyst h, and the gas space velocity of the synthesis gas in the reaction system is 1500mL _syngas /mL _catalyst ·h, the reaction time was 60h, the tail gas was analyzed by on-line gas chromatography, and the liquid product was sampled from the collection tank and analyzed by on-line gas chromatography. The hydroformylation of mixed isomers of octene has a conversion rate of 96.5% and a selectivity of 92.8%.

Example 2

Weigh 1.0 g (about 1.5 mL) of the above-mentioned catalyst 5Rh/POP catalyst with a loading of 5‰ and put it into the constant temperature zone of the fixed-bed reactor. Firstly, syngas was introduced into the reaction system, and after purging for 10 min, the temperature was raised to 100 °C at a rate of 10 °C/min, and the pressure was increased to 3.0 MPa, waiting for the system to stabilize. Then the mixed octene is pumped into the mixer through a high-pressure pump, the weight hourly space velocity of the mixed octene is adjusted to be 0.02 g _{mixed octene} /g _catalyst h, and the gas space velocity of the synthesis gas in the reaction system is 1500mL _{synthesis gas} /mL _catalyst ·h, the reaction time is 1000h, the tail gas is analyzed by online gas chromatography, and the liquid product is sampled from the collection tank and analyzed by online gas chromatography. In the hydroformylation reaction of mixed isomerized octene, the conversion rate is maintained above 93.2%, the selectivity is above 92.0%, and there is no obvious deactivation of the catalyst.

Example 3

0.5 g (about 0.75 mL) of the above-mentioned catalyst 1Rh/POP catalyst with a loading of 1‰ was weighed and loaded into the constant temperature zone of the fixed bed reactor. Firstly, syngas was introduced into the reaction system, and after purging for 10 min, the temperature was raised to 130 °C at a rate of 10 °C/min, and the pressure was increased to 3.0 MPa, waiting for the system to stabilize. Then, the mixed octene is pumped into the mixer through a high-pressure pump, and the liquid mass space velocity of the mixed octene is adjusted to be 0.1 g _{mixed octene} /g _catalyst h, and the gas volume of the synthesis gas in the reaction system is empty. The reaction was carried out at a rate of 1500 mL _syngas /mL _catalyst h, and the reaction time was 60 h. The tail gas was analyzed by on-line gas chromatography, and the liquid product was sampled from the collection tank and analyzed by gas chromatography. Hydroformylation of mixed isomers of octene, the conversion rate is 28.5%, and the selectivity is 95.2%.

Example 4

0.5 g (about 0.75 mL) of the above-mentioned catalyst 1Rh/POP catalyst with a loading of 1‰ was weighed and loaded into the constant temperature zone of the fixed bed reactor. Firstly, syngas was introduced into the reaction system, and after purging for 10 min, the temperature was raised to 100 °C at a rate of 10 °C/min, and the pressure was increased to 7.0 MPa, waiting for the system to stabilize. Then, the mixed octene is pumped into the mixer through a high-pressure pump, and the liquid mass space velocity of the mixed octene is adjusted to be 0.1 g _{mixed octene} /g _catalyst h, and the gas volume of the synthesis gas in the reaction system is empty. The reaction was carried out at a rate of 1500 mL _syngas /mL _catalyst h, and the reaction time was 60 h. The tail gas was analyzed by on-line gas chromatography, and the liquid product was sampled from the collection tank and analyzed by gas chromatography. The hydroformylation of mixed isomers of octene has a conversion rate of 23.5% and a selectivity of 95.5%.

Example 5

Weigh 0.5 g (about 0.75 mL) of the above-mentioned catalyst 2.5Rh/POP catalyst with a loading of 2.5‰ and put it into the constant temperature position of the fixed bed reactor. Firstly, syngas was introduced into the reaction system, and after purging for 10 min, the temperature was raised to 100 °C at a rate of 10 °C/min, and the pressure was increased to 3.0 MPa, waiting for the system to stabilize. Then, the mixed octene is pumped into the mixer through a high-pressure pump, and the liquid mass space velocity of the mixed octene is adjusted to be 0.02 g _{mixed octene} /g _catalyst h, and the gas volume of the synthesis gas in the reaction system is empty. The reaction was carried out at a rate of 1500 mL _syngas /mL _catalyst h, and the reaction time was 60 h. The tail gas was analyzed by on-line gas chromatography, and the liquid product was sampled from the collection tank and analyzed by gas chromatography. Mixed iso-octene hydroformylation reaction, conversion rate of 80.5%, selectivity of 93.9%.

Example 6

In the oxidation reactor, 10 mL of isononanal prepared in Example 1 was added to the oxidation reactor body, and the gas in the oxidation reactor was replaced with an inert gas. Before the reaction starts, the oxidation reactor body is heated by the heat exchanger. When the temperature in the oxidation reactor body rises to 70 ° C, the stirring speed is turned on to be 200 rpm, and the oxygen-containing gas O ₂ /N ₂ (O ₂ concentration 21v/v%) storage tank valve, make it pass into the isononanal reaction liquid in the oxidation reactor body by bubbling at a flow rate of 50 mL/min and through a bubble distributor, so that it is in the isononanal reaction liquid The pressure in the oxidizer body is adjusted to 1 atm through the back pressure valve. After 2 h of reaction, stirring and oxygen supply were stopped. A small amount of the reaction product was diluted in methanol solvent, and a certain amount of ethanol was added as an internal standard. The chromatographic analysis showed that the conversion of isononanoal was 95.2%, and the selectivity of isononanoic acid was 98.5%.

Example 7

Compared with Example 6, the difference is that the temperature in the oxidation reactor body is controlled at 80° C., and the chromatographic analysis shows that the conversion rate of isononanoal is 99.2%, and the selectivity of isononanoic acid is 97.3%.

Example 8

Compared with Example 6, the difference is that the temperature in the oxidation reactor body is controlled at 90° C., the chromatographic analysis shows that the conversion rate of isononanoal is 99.4%, and the selectivity of isononanoic acid is 92.5%.

Example 9

Compared with Example 6, the difference is that the temperature in the oxidation reactor body is controlled at 100° C., and the chromatographic analysis shows that the conversion rate of isononanoal is 99.4%, and the selectivity of isononanoic acid is 86.1%.

Example 10

Compared with Example 6, the difference is that the temperature in the oxidation reactor body is controlled at 60° C., and the chromatographic analysis shows that the conversion rate of isononanoal is 95.1%, and the selectivity of isononanoic acid is 97.5%.

Example 11

Compared with Example 6, the difference is that the temperature in the oxidation reactor is controlled at 30°C, the reaction time is extended to 6h, and the chromatographic analysis shows that the conversion rate of isononanoal is 90.6%, and the selectivity of isononanoic acid is 98.5%.

Example 12

Compared with Example 6, the difference is that the reaction time is extended to 6h, the chromatographic analysis shows that the conversion rate of isononanal is 99.6%, and the selectivity of isononanoic acid is 96.5%.

Example 13

Compared with Example 6, the difference is that the flow rate of the oxygen-containing gas is 20 mL/min, the chromatographic analysis shows that the conversion rate of isononanal is 93.6%, and the selectivity of isononanoic acid is 98.2%.

Example 14

Compared with Example 6, the difference is that the flow rate of the oxygen-containing gas is 80 mL/min, the chromatographic analysis shows that the conversion rate of isonononal is 96.8%, and the selectivity of isononanoic acid is 92.6%.

Example 15

Compared with Example 6, the difference is that the oxygen-containing gas O ₂ /N ₂ (O ₂ concentration of 21 v/v %) is replaced by pure oxygen (99.9 v/v %), the flow rate is 30 mL/min, and the chromatographic analysis The conversion rate of isononanoal was 96.4%, and the selectivity of isononanoic acid was 94.8%.

Example 16

Compared with Example 15, the difference is that the flow rate of pure oxygen is changed to 50 mL/min, the chromatographic analysis shows that the conversion rate of isononanoal is 96.8%, and the selectivity of isononanoic acid is 93.6%.

Example 17

Compared with Example 6, the difference is that the oxygen-containing gas O ₂ /N ₂ (O ₂ concentration is 21 v/v%) is replaced by O ₂ /N ₂ (O ₂ concentration is 50 v/v%), and the flow rate is 30mL/min, chromatographic analysis showed that the conversion rate of isonononal was 95.3%, and the selectivity of isononanoic acid was 95.2%.

Example 18

Compared with Example 6, the difference is that the amount of isononanal is 50 mL, the temperature is 80° C., and the reaction time is 6 h. The chromatographic analysis shows that the conversion of isononanal is 94.8%, and the selectivity of isononanoic acid is 98.2%.

Claims (9)

1. a method for preparing isononanoic acid by mixed isomerized octene, it is characterized in that, mixed isomerized octene takes place hydroformylation reaction under the effect of the Rh base catalyst of porous organic polymer immobilization to generate isononanoal, Then isononanoal reacts with oxygen-containing gas in the oxidation reactor under low temperature, low pressure and catalyst-free conditions to generate isononanoic acid; The specific process of the hydroformylation reaction is as follows: using a high-pressure pump to drive the liquid mixed isomerized octene into the reactor, and at a certain pressure and temperature, perform a hydroformylation reaction with synthesis gas in the presence of a catalyst to obtain isononyl. Aldehydes; the mixed iso-octene consists of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl- ₂ -pentene, the syngas is CO and H The catalyst is a highly dispersed heterogeneous solid catalyst composed of a main active component and a carrier, the main active component is Rh, and the carrier is a porous organic polymer, that is, a porous organic polymer-supported Rh-based catalyst ; The porous organic polymer is a polymer with rich hierarchical pore structure and large specific surface area, which is formed by the modification of organic ligands containing P and optional N or S functional elements through vinyl functional groups and then polymerized; The mass fraction of the main active components is 0.01% to 20%, and the rest are carriers; The oxidation reactor includes a reactor body, a flow controller, a bubble distributor, a stirrer, a back pressure valve, and a heat exchanger. The reactor body is provided with an inlet/outlet; the bubble distributor is arranged in the lower part of the reactor body , the stirring blade of the agitator is arranged at the lower part of the bubble distributor in the reactor body; the outlet of the oxygen-containing gas storage tank is provided with a pressure reducing valve and a pressure gauge, and the oxygen-containing gas storage tank is connected with the inlet of the flow controller through the first pipeline. The first pipeline is provided with a shut-off valve, the outlet of the flow controller is connected with the bubble distributor through the second pipeline; the back pressure valve is connected with the reactor body through the third pipeline, and the third pipeline is provided with a pressure gauge; the heat exchanger is located in The outer periphery and bottom of the reactor body; The specific process of the oxidation reaction is as follows: Step 1), a certain amount of isononanal is added into the oxidation reactor body through the liquid inlet/outlet, and the gas in the oxidation reactor is replaced with an inert gas; Step 2), heating the oxidation reactor body by the heat exchanger, so that the temperature in the oxidation reactor body is raised to a specified value; Step 3), the agitator is turned on; Step 4), the oxygen-containing gas controls the flow rate and flow rate through the flow controller, and is passed into the isononanal reaction solution by bubbling through the bubble distributor, so that it is evenly distributed in the isononanal reaction solution; through the back pressure The valve regulates the pressure in the oxidation reactor body; Step 5) After a certain time of reaction, stop stirring and oxygen supply, and take out the reaction product from the liquid inlet/outlet. 2. the method for preparing isononanoic acid by mixed isomer octene according to claim 1, is characterized in that, the described organic part containing P and optional N or S functional element is composed of one of the following parts one or several components:

3 . The method for preparing isononanoic acid from mixed iso-octene according to claim 1 , wherein the Rh-based catalyst supported by the porous organic polymer is prepared by dipping method or/and ultrasonic method. 4 . 4 . The method for preparing isononanoic acid from mixed isomerized octene according to claim 1 , wherein the _CO and H in the synthesis gas have a molar ratio of 1:10 to 100:1. 5 . 5. the method for preparing isononanoic acid by mixed isomer octene according to claim 1, is characterized in that, in the hydroformylation reaction, the reaction pressure is 0.1～30MPa, the reaction temperature is 50～200 ℃, and the mixed isomerism The weight hourly space velocity of octene is 0.01 to 20 h ^-1 , and the gas space velocity of synthesis gas is 1 to 10000 h ^-1 . 6 . The method for preparing isononanoic acid from mixed iso-octene according to claim 1 , wherein the reactor in the hydroformylation reaction is a fixed bed reactor or a slurry bed reactor. 7 . 7. the method for preparing isononanoic acid by mixed iso-octene according to claim 1, is characterized in that, the device used for preparing isonononal by mixed iso-octene comprises: high pressure pump, for pumping liquid mixed isooctene A mixer, which realizes the mixing of synthesis gas and mixed isooctene reaction material; a reactor, which is connected to the outlet of the mixer and is filled with a porous organic polymer-supported Rh-based catalyst to realize the mixing of isooctene. Heterogeneous catalytic reaction of carbonylation; product collection tank for collecting reaction products obtained from the reactor; online gas chromatography for analysis of tail gas and liquid products. 8. the method for preparing isononanoic acid by mixed iso-octene according to claim 1, is characterized in that, oxygen-containing gas is O ₂ /N ₂ , O ₂ /He, O ₂ /Ar or pure oxygen, O ₂ The concentration is 10 to 100 v/v%. 9. the method for preparing isononanoic acid by mixed isomer octene according to claim 1, is characterized in that, in the oxidation reaction, isonononal is in 5～20mL, and the flow rate of oxygen-containing gas is 5～100mL/min, and the reaction 20～100℃, 1～25atm, no catalyst for 1～20h.

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