CN111620772B - Production process for preparing isooctanoic acid by using isooctene aldehyde as raw material - Google Patents
Production process for preparing isooctanoic acid by using isooctene aldehyde as raw material Download PDFInfo
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Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a production process for preparing isooctanoic acid by taking isooctenal as a raw material. In a micro-bubble reactor, carrying out selective hydrogenation reaction by taking isooctenal as a raw material under the action of a nano particle hydrogenation catalyst to prepare isooctanal; adding the obtained isooctaldehyde into an oxidation reactor, blowing micro bubbles through an air generator, and reacting the isooctaldehyde with oxygen in the micro bubbles to obtain the isooctanoic acid. The production process has low cost, does not use high corrosive materials such as alkali, sulfuric acid, potassium permanganate and the like, does not generate environmental pollutants in the whole production process, and has strong environmental friendliness and good atom economy.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a production process for preparing isooctanoic acid by taking isooctenal as a raw material.
Background
Isooctanoic acid, also known as 2-ethylhexanoic acid, is a colorless, slightly odorous liquid, slightly soluble in cold water, soluble in hot water and diethyl ether, slightly soluble in ethanol, is an important fine chemical, and is widely used in the fields of coatings, inks, plastics, medicines, pesticides, national defense and the like. Isooctanoic acid is an alternative chemical to naphthenic acid, mostly used for the production of metal salts of isooctanoic acid. In general, isooctanoate has better performance than naphthenate and is more widely used.
At present, raw materials for synthesizing isooctanoic acid mainly comprise isooctenal, isooctylaldehyde and isooctyl alcohol. Isooctanoic acid is mainly used for preparing various metal salts as drier for coatings and paints, and its esters can be used as raw materials of plasticizer or carbenicillin. 2-ethyl caproic acid is mostly converted into salts of zirconium, cobalt, molybdenum, zinc and the like, and is used as a paint drier and a heat stabilizer of polyvinyl chloride plastics; tin salt is used as an additive of the plastic pipe; barium salt and cadmium salt are used for plastic rolling products and stabilizers, 2-ethylhexanoic acid and esters thereof are also used in the fields of medicines, bactericides, metal lubricants, cosmetics and the like, and glyceride thereof is an excellent plasticizer. 2-ethylhexanoic acid is a starting material for the pharmaceutical carbenicillin, used in the synthesis of many dyes, fragrances, and it is also an intermediate for paint and coating driers, used as an alkyd modifier, and the peroxide produced as a catalyst for polymerization reactions (e.g., PE), lubricating oil esters, and PVC stabilizers.
There are three main methods for the synthesis of 2-ethylhexanoic acid: (1) 2-ethylhexanol oxidation; (2) 2-ethylhexenal oxidation; (3) 2-ethyl hexanol dehydroesterification. The 2-ethylhexanol oxidation method is mainly characterized in that 2-ethylhexanol reacts with potassium permanganate in an alkaline or acidic medium to generate 2-potassium ethylhexanoate, and the potassium ethylhexanoate is acidified by concentrated sulfuric acid after being cooled to room temperature; the 2-ethylhexanol dehydrogenation esterification method is to use 2-ethylhexanol and sodium hydroxide to carry out oxidative dehydrogenation reaction to prepare 2-ethylhexanoic acid sodium, and then to neutralize with sulfuric acid to obtain isooctanoic acid. The two methods are both traditional processes, the scale of the device is small, and the three wastes are serious.
Chinese patent CN1817845A discloses a new process for preparing isooctanoic acid by a composite catalytic method, which comprises the steps of filling isooctanol and sodium hydroxide aqueous solution into a reaction kettle to ensure that the molar ratio of alcohol to alkali is 1.2-1.5; then adding a composite catalyst which is formed by combining 0.8-1.2 unit mass of calcium oxide, 0.6-0.9 unit mass of vanadium pentoxide and 0.1-0.4 unit mass of rare earth oxide under stirring; stirring and gradually addingThe temperature is increased to 240-280 ℃, so that the alcohol alkali oxidation reaction is finished after 1.8-2.2 hours; hydrogen gas is discharged; then cooling the reaction materials, adding 5-10% of water for dilution, and filtering out the solid composite catalyst; then adding H with the content of 30-40 percent 2 SO 4 The pH value of the materials is adjusted to 3 by the water solution, the materials are stirred for acidification reaction for 30 to 40 minutes, and the materials are kept stand for layering and the water layer is removed; then washing the material with water; and (5) carrying out reduced pressure dehydration to prepare an isooctanoic acid product. The patent belongs to a process for preparing isooctanoic acid by a 2-ethylhexanol oxidation method, the scale of a device is small, sodium hydroxide and sulfuric acid are required in the process, the corrosion to equipment is serious, a large amount of environmental pollutants are generated, and the problem of three wastes is serious.
Chinese patent CN107930647A discloses a catalyst, a preparation method thereof and a preparation method of 2-ethylhexanal. The preparation method of the 2-ethylhexanal comprises the following steps: heating the isooctene aldehyde feed to 180-220 ℃ to gasify the isooctene aldehyde, and introducing hydrogen into the isooctene aldehyde feed to obtain a mixed gas of gasified isooctene aldehyde and hydrogen; and the mixed gas is contacted with a catalyst in the hydrogenation reactor to carry out selective hydrogenation reaction, so as to obtain the mixed gas flow rich in 2-ethylhexanal. The patent has high hydrogenation temperature and large energy consumption, only obtains 2-ethylhexanal, and does not disclose the production process of the isooctanoic acid.
Chinese patent CN111054437A discloses a catalyst for preparing isooctylaldehyde by selective hydrogenation of isooctenal, a preparation method and application thereof. The catalyst is a metal-polymer composite catalyst and comprises a polyacid crosslinked polymer matrix and a metal active component, wherein the polyacid crosslinked polymer matrix is obtained by the coordination crosslinking action of the polymer matrix with a polyacid crosslinking agent. The method for preparing isooctylaldehyde comprises the following steps: in the presence of hydrogen, under the conditions of reaction temperature of 50-130 ℃ and reaction pressure of 1.0-5.0MPa, in a high-pressure kettle reactor, isooctyl aldehyde is obtained under the catalytic action of the metal-polymer composite catalyst. The catalyst of the patent requires sulfuric acid, phosphoric acid, peroxymolybdic acid and chloroplatinic acid during preparation, and three wastes are generated.
At present, the market of isooctanoic acid is in short supply, most of the isooctanoic acid is produced by an alcohol method at home, and the device scale is small. The isooctanoic acid produced by hydrogenation and oxidation of isooctenal has the advantages of low consumption, little pollution, stable product quality, etc. Therefore, a production process for preparing isooctanoic acid from isooctenal by utilizing the advantages of isooctenal raw materials is needed to meet the growing demand of isooctanoic acid.
Disclosure of Invention
The invention aims to provide a production process for preparing isooctanoic acid by using isooctenal as a raw material, which has low production cost, does not use high-corrosive materials such as alkali, sulfuric acid, potassium permanganate and the like, and does not generate environmental pollutants in the whole production process.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the production process for preparing isooctanoic acid by using isooctenal as a raw material comprises the following steps:
(1) In a micro-bubble reactor, carrying out selective hydrogenation reaction by taking isooctenal as a raw material under the action of a nano particle hydrogenation catalyst to prepare isooctanal;
(2) Adding the isooctyl aldehyde obtained in the step (1) into an oxidation reactor, blowing micro bubbles through an air generator, and reacting the isooctyl aldehyde with oxygen in the micro bubbles to obtain the isooctanoic acid.
Wherein:
in the step (1), the nanoparticle hydrogenation catalyst is nanoparticles of gold, palladium, platinum, nickel, vanadium, molybdenum, manganese or oxides thereof; the molar ratio of the nanoparticle hydrogenation catalyst to the amount of isooctylaldehyde fed per hour is from 0.00008 to 0.01, preferably from 0.0001 to 0.009.
In the step (1), the temperature of the selective hydrogenation reaction is 30-170 ℃, preferably 80-160 ℃; the pressure is from 0.1 to 10MPa, preferably from 0.2 to 8MPa.
In the step (1), the space velocity of the isooctene aldehyde in the selective hydrogenation reaction process is 0.005-1h -1 Preferably 0.01 to 0.9h -1 (ii) a The feed molar ratio of isooctenal to hydrogen is 1.
In the step (2), the isooctyl aldehyde enters an oxidation reactor for reaction, and the space velocity of the isooctyl aldehyde is 0.005-1h -1 Preferably 0.01 to 0.9h -1 (ii) a The reaction temperature of the isooctyl aldehyde in the oxidation reactor is 20-150 ℃, and the preferred temperature is 30-120 ℃; the feed molar ratio of isooctylaldehyde to oxygen is 1.
The production process for preparing isooctanoic acid by using isooctenal as a raw material comprises the following steps:
(1) In a micro-bubble reactor, carrying out selective hydrogenation reaction by taking isooctenal as a raw material under the action of a nano particle hydrogenation catalyst to prepare isooctanal;
(2) Mixing the isooctyl aldehyde obtained in the step (1) with an oxidation catalyst, adding the mixture into an oxidation reactor, blowing micro bubbles through an air generator, and reacting the isooctyl aldehyde with oxygen in the micro bubbles to obtain isooctanoic acid; the oxidation catalyst is recovered with the mother liquor after being filtered by a filter at an isooctanoic acid outlet for recycling.
Wherein:
in the step (2), the oxidation catalyst is cobalt acetate, molybdenum acetate, silver acetate, manganese isooctanoate, cobalt isooctanoate, molybdenum isooctanoate, silver isooctanoate, manganese dioxide, silver oxide, vanadium acetylacetonate, molybdenum trioxide, vanadium pentoxide, aluminum oxide, ferric chloride or palladium oxide;
the molar ratio of oxidation catalyst to isooctylaldehyde feed per hour is from 0 to 0.1, preferably from 0 to 0.09.
Preferably, the production process for preparing the isooctanoic acid by using the isooctene aldehyde as the raw material comprises the following steps of:
(1) The microbubble reactor comprises a gas phase inlet, a liquid phase inlet, a microbubble tube and a reaction zone, wherein the microbubble tube, the gas phase inlet and the liquid phase inlet are positioned at the upper part of the reaction zone, an annular space channel is formed between the microbubble tube and the tube wall of the microbubble reactor, the liquid phase inlet is connected with the annular space channel, and the gas phase inlet is connected with the microbubble tube; a nano particle hydrogenation catalyst is arranged inside the reaction zone, and a heating medium channel is arranged outside the reaction zone;
hydrogen enters the micro bubble tube from the gas phase inlet, isooctene aldehyde enters an annular channel formed between the micro bubble tube and the tube wall of the micro bubble reactor from the liquid phase inlet, the hydrogen penetrates through the micro bubble tube and carries out selective hydrogenation reaction with isooctene aldehyde under the action of a nano particle hydrogenation catalyst in a reaction zone to prepare isooctene aldehyde, and the isooctene aldehyde flows out from the bottom of the micro bubble reactor;
(2) An air generator is arranged at the bottom of the oxidation reactor, an air outlet is arranged at the top of the oxidation reactor, an isooctyl aldehyde inlet is arranged on one side surface of the oxidation reactor, an isooctanoic acid outlet is arranged on the other side surface of the oxidation reactor, the isooctanoic acid outlet is higher than the isooctyl aldehyde inlet, and a filter is arranged at the isooctanoic acid outlet; an insulating layer is arranged around the oxidation reactor;
and (2) enabling the isooctaldehyde obtained in the step (1) to enter an oxidation reactor from an isooctaldehyde inlet, blowing micro-bubbles through an air generator, enabling the isooctaldehyde to react with oxygen in the micro-bubbles to obtain isooctanoic acid, and enabling the isooctanoic acid to flow out of the oxidation reactor from an isooctanoic acid outlet.
Wherein: in the step (1), the microbubble reactor is an annular space flow fixed bed reactor; the width of the annular gap channel is 1-5mm, preferably 2-3mm; the micro bubble tube is made of a ceramic membrane, and the pore size of the ceramic membrane is 5-100nm, preferably 5-10nm; the length of the ceramic membrane is 5-100cm, preferably 20-30cm. The material of the micro bubble tube body can also be a metal film.
In the step (2), the air blowing pipes of the air generator are 1-10 groups, preferably 5-8 groups; the height of the air blast pipe is 5-100cm, preferably 50-60cm; the width between the air blowing tubes is 5-100cm, preferably 30-50cm.
And (2) introducing a heating medium into the heat-insulating layer for heat insulation, wherein the filter is a membrane filter.
The invention has the following beneficial effects:
the invention provides a production process for preparing isooctanoic acid by using isooctenal as a raw material, which is characterized in that the isooctenal is used as the raw material and is catalyzed by a nano particle hydrogenation catalyst in a microbubble reactor to carry out selective hydrogenation at a certain pressure, temperature and airspeed to prepare the isooctanal, and the obtained isooctanal can directly enter an oxidation system for oxidation reaction without purification.
In the microbubble reactor, hydrogen enters a microbubble tube and is dispersed into a large number of microbubbles to enter a liquid phase, the raw materials of isooctene aldehyde and hydrogen can carry out mass transfer and heat transfer under the micro-nano condition, and then catalytic hydrogenation is carried out on a nanoparticle hydrogenation catalyst micro interface, the reaction efficiency is high, the reaction selectivity is good, the reaction selectivity is not less than 95%, and the conversion rate is not less than 97%.
The obtained isooctyl aldehyde is added into an oxidation reactor, the periphery of the oxidation reactor is wrapped by a heating medium to ensure that the reaction is carried out at constant temperature, an air generator can generate a large amount of controllable micro bubbles, the control is carried out in real time according to the reaction condition, an air outlet is arranged at the upper part of the reactor to ensure that redundant gas is discharged, isooctyl aldehyde and an oxidation catalyst are uniformly mixed and then enter the oxidation reactor to be oxidized into isooctyl acid by oxygen in the micro bubbles, the product isooctyl acid is discharged at an outlet, the oxidation catalyst is recovered with mother liquor after the isooctyl acid is filtered by a filter at the outlet of the isooctyl acid and is recycled, the selectivity of the reaction is more than or equal to 94 percent, and the conversion rate is more than or equal to 97 percent.
The production process has low cost, does not use high-corrosivity materials such as alkali, sulfuric acid, potassium permanganate and the like, does not generate environmental pollutants in the whole production process, and has strong environmental friendliness and good atom economy.
Drawings
FIG. 1 is a schematic diagram of a microbubble reactor;
FIG. 2 is a schematic diagram of the structure of an oxidation reactor;
wherein: 1. a gas phase inlet; 2. a liquid phase inlet; 3. a micro bubble tube; 4. a nanoparticle hydrogenation catalyst; 5. a heating medium passage; 6. a reaction zone; 7. an air outlet; 8. an iso-octanal inlet; 9. an air generator; 10. a heat-insulating layer; 11. an isooctanoic acid outlet; 12. and (3) a filter.
Detailed Description
The present invention is further described below with reference to examples.
As shown in fig. 1 and 2, the microbubble reactor according to the present invention includes a gas phase inlet 1, a liquid phase inlet 2, a microbubble tube 3, and a reaction zone 6, wherein the microbubble tube 3, the gas phase inlet 1, and the liquid phase inlet 2 are located at an upper portion of the reaction zone 6, an annular gap channel is formed between the microbubble tube 3 and a tube wall of the microbubble reactor, the liquid phase inlet 2 is connected to the annular gap channel, and the gas phase inlet 1 is connected to the microbubble tube 3; a nano particle hydrogenation catalyst 4 is arranged inside the reaction zone 6, and a heating medium channel 5 is arranged outside the reaction zone 6;
the bottom of the oxidation reactor is provided with an air generator 9, the top of the oxidation reactor is provided with an air outlet 7, one side surface of the oxidation reactor is provided with an isooctyl aldehyde inlet 8, the other side surface of the oxidation reactor is provided with an isooctyl acid outlet 11, the isooctyl acid outlet 11 is higher than the isooctyl aldehyde inlet 8, and a filter 12 is arranged at the isooctyl acid outlet 11; an insulating layer 10 is also arranged around the oxidation reactor.
The microbubble reactor is an annular space flow fixed bed reactor; the width of the annular gap channel is 1-5mm; the micro bubble tube 3 is made of a ceramic membrane, the pore of the ceramic membrane is 5-100nm, and the length of the ceramic membrane is 5-100cm.
The air generator has 1-10 groups of air blowing pipes, the height of the air blowing pipes is 5-100cm, and the width between the air blowing pipes is 5-100cm.
Hydrogen enters a micro bubble tube 3 from a gas phase inlet 1, isooctene aldehyde enters an annular space channel formed between the micro bubble tube 3 and the tube wall of a micro bubble reactor from a liquid phase inlet 2, the hydrogen penetrates through the micro bubble tube 3 and carries out selective hydrogenation reaction with the isooctene aldehyde under the action of a nano particle hydrogenation catalyst 4 in a reaction zone 6 to prepare the isooctene aldehyde, and the isooctene aldehyde flows out from the bottom of the micro bubble reactor; the obtained isooctaldehyde enters the oxidation reactor from an isooctaldehyde inlet 8, micro-bubbles are blown in through an air generator 9, the isooctaldehyde reacts with oxygen in the micro-bubbles to prepare isooctanoic acid, and the isooctanoic acid flows out of the oxidation reactor from an isooctanoic acid outlet 11.
Example 1
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
subjecting the thus-obtained isomer toThe octanal enters an oxidation reactor, and the isooctyl aldehyde is oxidized into the isooctyl acid by oxygen in the microbubbles at the temperature of 70 ℃ through the microbubbles blown by the air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 2
The isooctenal enters a microbubble reactor, and is subjected to selective hydrogenation reaction with hydrogen under the pressure of 0.3MPa and the temperature of 130 ℃ and under the action of a palladium nanoparticle hydrogenation catalyst to produce the isooctenal, the selectivity of the reaction is 96.3 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 3
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 5MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 98.5 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feed molar ratio of the raw materials of isooctenal and hydrogen is1, the molar ratio of the use amount of the palladium nanoparticle hydrogenation catalyst to the feed amount of isooctene aldehyde per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 4
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 90 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 98.6 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 5
Introducing isooctylaldehyde into a microbubble reactor at 1MPa and 170 deg.CUnder the action of the palladium nanoparticle hydrogenation catalyst, the isooctenal and hydrogen undergo selective hydrogenation reaction to produce isooctylaldehyde, the selectivity of the reaction is 97.1%, and the conversion rate is 99%. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 6
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a nickel nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce isooctene aldehyde, the selectivity of the reaction is 95.9%, and the conversion rate is 98%. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of a nickel nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of the isooctylaldehyde to the oxygen is 1The number of the air blowing tubes of the generator was 8, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 7
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a molybdenum nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 96.3 percent, and the conversion rate is 97 percent. Wherein the space velocity of the raw material isooctene aldehyde in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the molybdenum nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 8
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a platinum nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce isooctene aldehyde, the selectivity of the reaction is 97.5 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials namely isooctyl aldehyde and hydrogen is 1;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 9
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a vanadium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce isooctene aldehyde, the selectivity of the reaction is 97.9 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials isooctenal and hydrogen is 1, the molar ratio of the dosage of the vanadium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctyl aldehyde to oxygen is 1.
Example 10
The isooctenal enters a microbubble reactor, and is subjected to selective hydrogenation reaction with hydrogen under the pressure of 1MPa and the temperature of 130 ℃ and under the action of a palladium oxide nanoparticle hydrogenation catalyst to produce the isooctenal, the selectivity of the reaction is 96.6 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 Starting from isooctenal and hydrogenThe feeding molar ratio of gas is 1;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 11
The isooctenal enters a microbubble reactor, and is subjected to selective hydrogenation reaction with hydrogen under the pressure of 1MPa and the temperature of 130 ℃ and under the action of a nickel oxide nano particle hydrogenation catalyst to produce the isooctenal, the selectivity of the reaction is 98.5 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctene aldehyde in the reactor is 0.1h -1 The feeding molar ratio of raw materials isooctenal and hydrogen is 1;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 12
The iso-octenal has slight entranceIn a bubble reactor, under the pressure of 1MPa and the temperature of 130 ℃ and the action of a molybdenum oxide nano particle hydrogenation catalyst, the isooctyl aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctyl aldehyde, wherein the selectivity of the reaction is 98.8 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials isooctenal and hydrogen is 1;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 13
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 98.5 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.02h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 Iso octyl aldehydeAnd oxygen at a feed molar ratio of 1, 8 sets of aeration tubes in the air generator of the oxidation reactor, a height of 60cm, a width between the aeration tubes of 35cm, a selectivity of the reaction of 98.0%, and a conversion of 100%.
Example 14
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 97.9 percent, and the conversion rate is 97 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.9h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctyl aldehyde to oxygen is 1.
Example 15
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 96.9 percent, and the conversion rate is 98 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001The length of the membrane is 25cm;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctyl aldehyde to oxygen is 1.
Example 16
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 98.9 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1:20, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 17
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 96.8 percent, and the conversion rate is 98 percent. Wherein the raw material isooctenal is in a reactorSpace velocity of 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.0005;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 18
The isooctene aldehyde enters a micro-bubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 98.8 percent, and the conversion rate is 99 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the consumption of a palladium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.008;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 98.0%, and the conversion was 100%.
Example 19
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 50 ℃ through the micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 96.5%, and the conversion was 98%.
Example 20
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 120 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctylaldehyde in the reactor is0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air-blowing tubes of the air generator in the oxidation reactor, the height of the air-blowing tubes was 60cm, the width between the air-blowing tubes was 35cm, the selectivity of the reaction was 95.9%, and the conversion was 98%.
Example 21
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctene aldehyde in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.02h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 97.6%, and the conversion was 98%.
Example 22
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa, the temperature of 130 ℃ and the action of a palladium nano particle hydrogenation catalyst, the isooctene aldehyde and hydrogen are subjected to selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001The pore space of the ceramic membrane is 10nm, and the length of the ceramic membrane is 25cm;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.8h -1 The feeding molar ratio of isooctyl aldehyde to oxygen is 1.
Example 23
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, 8 sets of air blowing tubes of the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 96.1%, and the conversion was 97%.
Example 24
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. In which the original siteThe space velocity of the material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The molar ratio of the isooctyl aldehyde to the oxygen fed was 1:20, 8 sets of air blowing tubes in the air generator in the oxidation reactor, the height of the air blowing tubes was 60cm, the width between the air blowing tubes was 35cm, the selectivity of the reaction was 96.3%, and the conversion was 98%.
Example 25
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials namely isooctyl aldehyde and hydrogen is 1;
uniformly mixing the obtained isooctyl aldehyde and a manganese acetate oxidation catalyst, then feeding the mixture into an oxidation reactor, and oxidizing the isooctyl aldehyde into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of the isooctanal to the oxygen is 1,the width between the sparge tubes was 35cm, the selectivity of the reaction was 95.6%, and the conversion was 99%.
Example 26
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
uniformly mixing the obtained isooctyl aldehyde and a manganese acetate oxidation catalyst, then feeding the mixture into an oxidation reactor, and oxidizing the isooctyl aldehyde into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feed molar ratio of isooctanal to oxygen was 1, the molar ratio of the amount of manganese acetate oxidation catalyst to the amount of isooctanal fed per hour was 0.005, 8 sets of air tubes of the air generator in the oxidation reactor, the height of the air tubes was 60cm, the width between the air tubes was 35cm, the selectivity of the reaction was 94.9%, and the conversion was 98%.
Example 27
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctene aldehyde in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001The length of the ceramic membrane is 25cm;
uniformly mixing the obtained isooctyl aldehyde and a cobalt acetate oxidation catalyst, then feeding the mixture into an oxidation reactor, and oxidizing the isooctyl aldehyde into isooctanoic acid by oxygen in microbubbles at the temperature of 70 ℃ through microbubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctyl aldehyde to oxygen is 1.
Example 28
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.5 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
uniformly mixing the obtained isooctyl aldehyde and a cobalt acetate oxidation catalyst, then feeding the mixture into an oxidation reactor, and oxidizing the isooctyl aldehyde into isooctanoic acid by oxygen in microbubbles at the temperature of 70 ℃ through microbubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The molar ratio of the fed isooctyl aldehyde to oxygen was 1.
Example 29
The isooctene aldehyde enters the micro-gasIn a bubble reactor, under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, isooctylaldehyde and hydrogen undergo a selective hydrogenation reaction to produce isooctylaldehyde, wherein the selectivity of the reaction is 99.1 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the feeding amount of isooctenal per hour is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 The feeding molar ratio of isooctylaldehyde to oxygen was 1, the number of blowing tubes of the air generator in the oxidation reactor was 4, the height of the blowing tubes was 30cm, the width between the blowing tubes was 55cm, the selectivity of the reaction was 98.2%, and the conversion was 99%.
Example 30
The isooctene aldehyde enters a microbubble reactor, and under the pressure of 1MPa and the temperature of 130 ℃ and the action of a palladium nanoparticle hydrogenation catalyst, the isooctene aldehyde and hydrogen undergo a selective hydrogenation reaction to produce the isooctene aldehyde, wherein the selectivity of the reaction is 99.3 percent, and the conversion rate is 100 percent. Wherein the space velocity of the raw material isooctenal in the reactor is 0.1h -1 The feeding molar ratio of raw materials of isooctenal and hydrogen is 1, the molar ratio of the dosage of the palladium nanoparticle hydrogenation catalyst to the hourly feeding amount of isooctenal is 0.001;
the obtained isooctyl aldehyde enters an oxidation reactor, and is oxidized into isooctyl acid by oxygen in micro-bubbles at the temperature of 70 ℃ through micro-bubbles blown by an air generator; the space velocity of the isooctyl aldehyde in the reactor is 0.1h -1 Introduction of isooctanal and oxygenThe molar ratio of the materials is 1.
Claims (9)
1. A production process for preparing isooctanoic acid by using isooctene aldehyde as a raw material is characterized by comprising the following steps:
(1) Carrying out selective hydrogenation reaction in a microbubble reactor by taking isooctene aldehyde as a raw material under the action of a nanoparticle hydrogenation catalyst to prepare isooctene aldehyde;
(2) Feeding the isooctyl aldehyde obtained in the step (1) into an oxidation reactor, blowing micro-bubbles through an air generator, and reacting the isooctyl aldehyde with oxygen in the micro-bubbles to obtain isooctanoic acid;
in the step (1), the nanoparticle hydrogenation catalyst is nanoparticles of gold, palladium, platinum, nickel, vanadium, molybdenum, manganese or oxides thereof; the molar ratio of the nanoparticle hydrogenation catalyst to the isooctenal feeding amount per hour is 0.00008-0.01;
the microbubble reactor comprises a gas phase inlet (1), a liquid phase inlet (2), a microbubble tube (3) and a reaction zone (6), the microbubble tube (3), the gas phase inlet (1) and the liquid phase inlet (2) are positioned at the upper part of the reaction zone (6), an annular gap channel is formed between the microbubble tube (3) and the tube wall of the microbubble reactor, the liquid phase inlet (2) is connected with the annular gap channel, and the gas phase inlet (1) is connected with the microbubble tube (3); a nano particle hydrogenation catalyst (4) is arranged in the reaction zone (6), and a heating medium channel (5) is arranged outside the reaction zone (6);
an air generator (9) is arranged at the bottom of the oxidation reactor, an air outlet (7) is arranged at the top of the oxidation reactor, an isooctyl aldehyde inlet (8) is arranged on one side surface of the oxidation reactor, an isooctyl acid outlet (11) is arranged on the other side surface of the oxidation reactor, the isooctyl acid outlet (11) is higher than the isooctyl aldehyde inlet (8), and a filter (12) is arranged at the isooctyl acid outlet (11); an insulating layer (10) is also arranged around the oxidation reactor.
2. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 1, characterized in that: in the step (1), the temperature of the selective hydrogenation reaction is 30-170 ℃, and the pressure is 0.1-10MPa.
3. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 1, characterized in that: in the step (1), the space velocity of the isooctene aldehyde in the selective hydrogenation reaction process is 0.005-1h -1 The feeding molar ratio of the isooctenal to the hydrogen is 1.
4. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 1, characterized in that: in the step (2), the isooctyl aldehyde enters an oxidation reactor for reaction, and the space velocity of the isooctyl aldehyde is 0.005-1h -1 The feeding molar ratio of the isooctyl aldehyde to the oxygen is 1; the reaction temperature of the isooctyl aldehyde in the oxidation reactor is 20-150 ℃.
5. The process for preparing isooctanoic acid from isooctenal as claimed in any one of claims 1 to 4, wherein the process comprises the steps of: the method comprises the following steps:
(1) Carrying out selective hydrogenation reaction in a microbubble reactor by taking isooctene aldehyde as a raw material under the action of a nanoparticle hydrogenation catalyst to prepare isooctene aldehyde;
(2) Mixing the isooctaldehyde obtained in the step (1) with an oxidation catalyst, then feeding the mixture into an oxidation reactor, blowing micro bubbles through an air generator, and reacting the isooctaldehyde with oxygen in the micro bubbles to obtain the isooctanoic acid.
6. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 5, wherein: in the step (2), the oxidation catalyst is cobalt acetate, molybdenum acetate, silver acetate, manganese isooctanoate, cobalt isooctanoate, molybdenum isooctanoate, silver isooctanoate, manganese dioxide, silver oxide, vanadium acetylacetonate, molybdenum trioxide, vanadium pentoxide, aluminum oxide, ferric chloride or palladium oxide; the molar ratio of the oxidation catalyst to the amount of isooctylaldehyde fed per hour is 0-0.1.
7. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 5, wherein: the method comprises the following steps:
the microbubble reactor (1) comprises a gas phase inlet (1), a liquid phase inlet (2), a microbubble tube (3) and a reaction zone (6), wherein the microbubble tube (3), the gas phase inlet (1) and the liquid phase inlet (2) are positioned at the upper part of the reaction zone (6), an annular space channel is formed between the microbubble tube (3) and the tube wall of the microbubble reactor, the liquid phase inlet (2) is connected with the annular space channel, and the gas phase inlet (1) is connected with the microbubble tube (3); a nano particle hydrogenation catalyst (4) is arranged in the reaction zone (6), and a heating medium channel (5) is arranged outside the reaction zone (6);
hydrogen enters a micro bubble tube (3) from a gas phase inlet (1), isooctene aldehyde enters an annular space channel formed between the micro bubble tube (3) and the tube wall of a micro bubble reactor from a liquid phase inlet (2), the hydrogen penetrates through the micro bubble tube (3) and carries out selective hydrogenation reaction with isooctene aldehyde under the action of a nano particle hydrogenation catalyst (4) in a reaction zone (6) to prepare isooctene aldehyde, and the isooctene aldehyde flows out of the bottom of the micro bubble reactor;
(2) An air generator (9) is arranged at the bottom of the oxidation reactor, an air outlet (7) is arranged at the top of the oxidation reactor, an isooctyl aldehyde inlet (8) is arranged on one side surface of the oxidation reactor, an isooctanoic acid outlet (11) is arranged on the other side surface of the oxidation reactor, the isooctanoic acid outlet (11) is higher than the isooctyl aldehyde inlet (8), and a filter (12) is arranged at the isooctanoic acid outlet (11); an insulating layer (10) is also arranged around the oxidation reactor;
and (2) enabling the isooctaldehyde obtained in the step (1) to enter an oxidation reactor from an isooctaldehyde inlet (8), blowing micro-bubbles through an air generator (9), enabling the isooctaldehyde to react with oxygen in the micro-bubbles to prepare isooctanoic acid, and enabling the isooctanoic acid to flow out of the oxidation reactor from an isooctanoic acid outlet (11).
8. The production process for preparing isooctanoic acid from isooctenal as claimed in claim 7, wherein: in the step (1), the microbubble reactor is an annular space flow fixed bed reactor; the width of the annular gap channel is 1-5mm; the micro-bubble tube (3) is made of a ceramic membrane, the pores of the ceramic membrane are 5-100nm, and the length of the ceramic membrane is 5-100cm.
9. The process of claim 7 for preparing isooctanoic acid from isooctanal comprises the following steps: in the step (2), the air blowing pipes of the air generator are 1-10 groups, the height of the air blowing pipes is 5-100cm, and the width between the air blowing pipes is 5-100cm.
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| SU1697381A1 (en) * | 1990-04-28 | 1997-02-27 | Ленинградское научно-производственное объединение по разработке и внедрению нефтехимических процессов "Леннефтехим" | Method for production of 2-ethylhexylic acid |
| CN106237966A (en) * | 2016-08-23 | 2016-12-21 | 南京大学 | The reactor of aromatic aldehyde is produced for the oxidation of toluene class material |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
| CN109225073A (en) * | 2018-09-17 | 2019-01-18 | 清华大学 | Hydrogenation reaction device and its method for carrying out hydrogenation reaction in a kind of micro- packed bed |
| CN109679690A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of liquid-phase hydrogenatin system and liquid phase hydrogenating method |
| CN111054437A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing isooctylaldehyde through selective hydrogenation of isooctenal, preparation method and application |
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| SU1697381A1 (en) * | 1990-04-28 | 1997-02-27 | Ленинградское научно-производственное объединение по разработке и внедрению нефтехимических процессов "Леннефтехим" | Method for production of 2-ethylhexylic acid |
| CN106237966A (en) * | 2016-08-23 | 2016-12-21 | 南京大学 | The reactor of aromatic aldehyde is produced for the oxidation of toluene class material |
| CN109679690A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of liquid-phase hydrogenatin system and liquid phase hydrogenating method |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
| CN109225073A (en) * | 2018-09-17 | 2019-01-18 | 清华大学 | Hydrogenation reaction device and its method for carrying out hydrogenation reaction in a kind of micro- packed bed |
| CN111054437A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing isooctylaldehyde through selective hydrogenation of isooctenal, preparation method and application |
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