CN110922328A - Method for treating heavy components in crude isooctanoic acid product - Google Patents
Method for treating heavy components in crude isooctanoic acid product Download PDFInfo
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- CN110922328A CN110922328A CN201911275496.2A CN201911275496A CN110922328A CN 110922328 A CN110922328 A CN 110922328A CN 201911275496 A CN201911275496 A CN 201911275496A CN 110922328 A CN110922328 A CN 110922328A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for treating heavy components in an isooctanoic acid crude product, which comprises the steps of mixing the heavy components in the isooctanoic acid crude product obtained by oxidizing isooctaldehyde with water and an alkali metal salt auxiliary agent, then carrying out contact reaction with a solid super acidic catalyst, and carrying out oil-water two-phase separation on a reaction product to obtain an oil phase and a water phase. The water phase can be recycled, and the oil phase can be used as an oxidation reaction catalyst and added into the oxidation reaction again. The method can effectively recover the catalyst and the isooctanoic acid product in the heavy component, effectively improve the yield of the isooctanoic acid, and greatly reduce the use amount of the catalyst and the production amount of the heavy component waste liquid.
Description
Technical Field
The invention relates to the technical field of preparation of isooctanoic acid, in particular to a method for treating heavy components in a crude product of isooctanoic acid.
Background
Isooctanoic acid is an important organic chemical product, can be widely used in the fields of coating, plastics, leather, medicine, wood, chemical fiber, pesticide and the like, but is mostly used for producing metal salt of isooctanoic acid. The isooctoate has a more obvious drying effect than naphthenate, so that the isooctoate is widely used in the coating industry to meet the requirements of people on high-grade light-colored coatings. Isooctanoic acid is mainly used as a salifying reagent for synthesizing penicillin sodium salt by a solvent method in the aspect of medicine. In addition, the glyceryl isooctanoate is an excellent plasticizer, and with the development of industry and agriculture, the demand of the isooctanoic acid is increased year by year, so that the glyceryl isooctanoate has great development potential.
The isooctanoic acid industrialized synthesis mainly has two routes, one is isooctanol oxidation method, although the method has high selectivity, reliable raw material source and simple operation, the process flow is long, the three wastes energy consumption is higher, the intermittent operation is not easy to produce in large scale; secondly, n-butyl aldehyde is used as a raw material, 2-ethyl hexenal is generated through condensation and dehydration, isooctyl aldehyde is obtained through hydrogenation, and isooctyl acid is obtained through oxidation. The 2-ethyl hexenal in the aldehyde oxidation process is an intermediate for producing isooctyl alcohol, the raw material source is reliable, the process is a continuous and totally-closed process, large-scale production is easy, and some major companies in Europe and America adopt the route for production.
The oxidation reaction is surrounded by the related technology of preparing isooctanoic acid by oxidizing isooctylaldehyde, such as CN13575A process for producing 2-ethylhexanoic acid is disclosed in the patent publication 27A, which discloses an optimum reaction temperature of 0 to 15 ℃ and a maximum selectivity of 94.9%, but a low reaction temperature and a high energy consumption; CN1410407A discloses a method for producing 2-ethyl hexanoic acid, which overcomes the disadvantages of the previous patent and changes the optimal reaction temperature to 30-50 ℃ and the reaction equipment from a bubble column to a falling film reactor, but the investment cost of industrial production equipment is high and the selectivity is not obviously improved. CN1422840A discloses a method for preparing 2-ethyl caproic acid, which changes reaction equipment into a reaction tower, greatly shortens the reaction time, has the highest selectivity of 96.8 percent, but has troublesome post-treatment of a catalyst. The catalyst used in the above 3 patent applications is Mn (OAc)2Or KOAc or Cu (OAc)2Or NaOAc or a mixture of these four substances in any ratio, the selectivity is not very satisfactory, and no post-treatment process of the catalyst is reported, with low overall yields.
CN102701944A discloses a method for preparing 2-ethyl hexanoic acid by catalyzing and oxidizing 2-ethyl hexanal with phosphomolybdovanadate. The patent application relates to a preparation method of a chemical preparation, the selectivity of 2-ethyl hexanoic acid can reach more than 98%, although a solid catalyst is convenient to separate, the preparation of the catalyst needs molybdate, phosphate, metavanadate, concentrated sulfuric acid, hydrochloric acid and the like, the preparation process is complex, the regeneration is difficult, and the preparation method has a long distance from industrial application.
U.S. Pat. No. 5,983,1187 discloses that the alkali metal-containing distillation residue obtained after distillation of α -alkyl-branched carboxylic acids can be reused for the oxidation of aldehydes, but the color of the product decreases after direct recycle oxidation, and the product index cannot be met.
CN104114527B discloses a method for recovering aliphatic monocarboxylic acid with 4 to 11 carbon atoms from distillation residue, which comprises reacting the distillation residue with an acidic aqueous solution to convert aliphatic monocarboxylic acid salt into monocarboxylic acid and obtain a salt-containing aqueous solution, wherein the method can effectively recover the aliphatic monocarboxylic acid in the distillation residue and improve the product yield, but simultaneously generate acidic salt-containing wastewater, the catalyst needs to be continuously supplemented, the post-treatment is complicated, and the requirement for equipment material of the acidolysis process is high.
As described above, in the conventionally disclosed technology for producing isooctanoic acid by oxidation of isooctylaldehyde, a metal salt is often used as a homogeneous catalyst for the oxidation reaction, but there are problems in handling of a heavy component solution containing a catalyst produced by separation of the reaction solution.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for treating heavy components in an isooctanoic acid crude product, which can effectively recover a catalyst and an isooctanoic acid product in the heavy components, effectively improve the yield of isooctanoic acid, and greatly reduce the usage amount of the catalyst and the production amount of heavy component waste liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for treating heavy components in an isooctanoic acid crude product, which comprises the steps of mixing the heavy components in the isooctanoic acid crude product obtained by oxidizing isooctyl aldehyde with water and an alkali metal salt auxiliary agent, then carrying out contact reaction with a solid super acidic catalyst, carrying out oil-water two-phase separation on the obtained reaction product, and circulating the obtained oil phase serving as a catalyst to a reaction system for preparing isooctanoic acid by oxidizing isooctyl aldehyde; wherein the solid super acidic catalyst is sulfate ion acidic SO doped with metal elements4 2-/MxOyA bimetallic oxide. Wherein M isxOyThe bimetallic oxide is used as a carrier, M is selected from one or more of zirconium, aluminum, titanium, iron and tin, x is 1 or 2, and y is 2 or 3.
According to the method of the invention, in a preferred embodiment, the heavy component in the crude product is obtained by carrying out oxidation reaction on isooctanal and air in the presence of a metal salt catalyst to obtain an isooctanoic acid crude product, and then rectifying and separating the isooctanoic acid crude product to respectively obtain a solution of a light component, isooctanoic acid and the heavy component; preferably, the solution of the heavy component comprises, by mass, 5-40% of a metal salt compound, 55-90% of isooctanoic acid and 1-10% of isooctanoate, isooctanoic anhydride and isooctanoic acid isomer. The light component comprises butyraldehyde, isooctylaldehyde, 3-heptanone, 3-heptyl formate and other substances with the boiling point lower than that of isooctanoic acid.
The heavy component solution contains metal salt compounds, when the concentration of the isooctanoic acid is too low, the viscosity of the solution is obviously increased, and the concentration of the isooctanoic acid in the component is generally not lower than 55%. Isooctanoate and isooctanoic anhydride are produced during the reaction and separation, wherein isooctanoate is isooctyl isooctanoate and 3-heptyl isooctanoate.
According to the method of the invention, the metal salt catalyst is preferably a metal salt of isooctanoic acid, the metal element is preferably one or more of sodium, potassium, iron, copper, manganese, cobalt and palladium, and is further preferably sodium isooctanoate, a mixture of sodium isooctanoate and manganese isooctanoate and/or a mixture of potassium isooctanoate and cobalt isooctanoate. The dosage of the metal salt catalyst is preferably 0.5-5%, more preferably 1-3% of the mass of the raw material isooctyl aldehyde.
In a preferred embodiment, the oxidation reaction according to the process of the invention is carried out at a temperature of from 5 to 50 ℃, preferably from 10 to 40 ℃; the reaction pressure (absolute pressure) is from 0.1 to 0.5MPa, preferably from 0.1 to 0.3MPa, more preferably 0.1 MPa; the molar ratio of isooctylaldehyde to oxygen in air is 1-2:1, preferably 1.4 to 1.8: 1; the residence time is 10-50h, preferably 15-40 h.
In a preferred embodiment of the process according to the invention, the separation by distillation of the crude isooctanoic acid is carried out by: a pressure of 0.5 to 5kPa, preferably 1 to 2 kPa; a theoretical plate number of 10 to 30, preferably 15 to 25; the reflux ratio is from 0.5 to 2.5:1, preferably from 1 to 2: 1.
According to the process of the invention, the amount of water mixed with the heavies solution is preferably 10 to 40%, preferably 20 to 30%, of the weight of the heavies solution. Water reacts with the esters therein.
According to the method of the invention, the alkali metal salt auxiliary agent is preferably an alkali metal sulfate and/or bisulfate, such as sodium sulfate, potassium sulfate, lithium bisulfate and the like, and the addition amount is 0.1-5%, preferably 1-2% of the water amount in terms of mass fraction.
According to the method of the invention, the mixed solution of the heavy components, water and the alkali metal salt auxiliary agent is fedThe liquid hourly space velocity (the ratio of the mass flow rate of the mixed solution of the heavy components, the water and the alkali metal salt auxiliary agent to the mass of the catalyst) is 0.01-0.02 h-1. The dosage of the solid super acidic catalyst is determined according to the flow of the heavy components and water to be treated.
According to the method of the present invention, the bimetallic oxide support has a nanosheet structure; the bimetallic oxide support is selected from ZrO2-Al2O3、TiO2-Al2O3、ZrO2-Fe2O3、TiO2-SnO2、Al2O3-Fe2O3、ZrO2-TiO2、ZrO2-SnO2、Al2O3-SnO2、TiO2-Fe2O3And SnO2-Fe2O3One or more of (a).
According to the method of the present invention, preferably, the metal element doped in the solid super acidic catalyst is one or more of yttrium, platinum, palladium and zinc.
According to the method of the invention, in a preferred embodiment, the method for preparing the support of the solid super acidic catalyst comprises: mixing two of zirconium tetrachloride, aluminum trichloride, titanium tetrachloride, ferric trichloride and stannic chloride with water, reacting for 2-6 h at 90-100 ℃, filtering, drying, and roasting for 2-4 h at 600 ℃ with 400-plus materials to obtain the white powder carrier.
According to the method of the invention, in a preferred embodiment, the method for preparing the support of the solid super acidic catalyst comprises: mixing two of zirconium tetrachloride, aluminum trichloride, titanium tetrachloride, ferric trichloride and tin tetrachloride with water, wherein the amount of the water is 8-12 times of the total mass of the chlorides, the molar ratio of any two metal elements in the chlorides is 0.7-1.4, adding ethylene glycol accounting for 40-60% of the mass of the chlorides into the mixture, reacting for 2-6 hours at 90-100 ℃, filtering, drying, and roasting for 2-4 hours at 400-600 ℃ to obtain the white powder carrier with the nanosheet structure. The dosage of each material in the preparation of the carrier is determined by the element proportion.
By adding ethylene glycol toThe surface of the carrier is introduced with a hydroxyl structure, and the obtained carrier has a large specific surface, for example, the specific surface area can reach 300-500 m2And/g, has a nano-lamellar structure. In addition, the bimetallic oxide carrier and the doped metal elements are adopted, so that the carbon deposition resistance of the catalyst is improved, the stability of the catalyst is improved, and the service life of the catalyst is prolonged.
According to the method of the invention, in a preferred embodiment, the method for preparing the solid super acid catalyst comprises: soaking the obtained carrier in a sulfuric acid aqueous solution, adding chloride selected from one or more of yttrium trichloride, platinum dichloride, palladium dichloride and zinc dichloride, wherein the concentration of sulfuric acid is 0.1-0.2mol/L, the using amount of the sulfuric acid solution is 15-25 times of the mass of the carrier according to mass fraction, the adding amount of the chloride is 0.01-0.05% of the mass of the sulfuric acid aqueous solution, soaking at 20-40 ℃ for 12-24 h, filtering, drying, and roasting at 400-600 ℃ for 2-4 h to obtain the solid super acidic catalyst.
In a preferred embodiment, the temperature for the contact reaction with the solid super acidic catalyst is 100-160 ℃, preferably 120-140 ℃; the reaction pressure is 0.1-1.0MPa, preferably 0.2-0.5 MPa; the residence time is 10-120min, preferably 30-60 min. The hydrolysis reaction is more thorough under the reaction conditions; the contact reaction with the solid super acidic catalyst is preferably carried out continuously in a tubular reactor. The continuous operation is adopted, the length diameter of the tubular reactor is larger, the specific surface is large, and the reaction contact is sufficient; the concrete structure is not limited, and the structure can be a single tube, can also be a conventional structure such as a plurality of tubes connected in parallel, and can also comprise a filling part or an internal member.
The isooctanoic acid ester substance and the isooctanoic anhydride in the heavy component solution are mixed with water and then undergo hydrolysis reaction under the action of a super-strong solid acid catalyst to produce the isooctanoic acid and the corresponding alcohol. Since the heavy component solution contains metal salt of isooctanoic acid, if acidic substances such as strong acid (such as sulfuric acid, hydrochloric acid) and cation exchange resin are used, the acidic substances and the metal salt of isooctanoic acid firstly undergo acidolysis reaction to generate isooctanoic acid and corresponding salt, and the function of ester substance hydrolysis cannot be realized. The alkali metal salt auxiliary agent is added, so that the hydrolysis of isooctoate in a heavy component solution and the falling-off of sulfate ions in the solid super acidic catalyst can be effectively inhibited, the catalytic effect of the oxidation catalyst which is recycled is ensured, and the service life of the solid super acidic catalyst is prolonged.
The heavy component solution is mixed with water and hydrolyzed under the catalysis of super-strong solid acid to obtain an oil-water two-phase, wherein the oil phase contains isooctanoic acid generated by hydrolysis, original isooctanoic acid, metal salt of isooctanoic acid, alcohol generated by hydrolysis and trace water, the process effectively improves the yield of isooctanoic acid, and a byproduct isooctanoate is effectively converted into isooctanoic acid; the water phase contains a small amount of isooctanoic acid, can be recycled, does not lose the isooctanoic acid in the process, and does not produce water phase waste liquid.
According to the method of the invention, the oil-water two-phase separation is preferably carried out in a chromatographic apparatus, the chromatographic apparatus is a conventional separation device in the field, and the structure is not described again; the temperature is preferably from 25 to 35 ℃. The oil phase containing the isooctanoic acid, the metal salt of the isooctanoic acid, the alcohol produced by hydrolysis and a little water is circulated to the oxidation reaction, wherein the metal salt of the isooctanoic acid is used as a catalyst, the isooctanoic acid is separated out in the subsequent separation process, and the yield of the isooctanoic acid is greatly improved; alcohol and trace water generated by hydrolysis are rectified and separated out as light components of the isooctanoic acid, and the quality of the product of the isooctanoic acid obtained after circulation is not reduced.
"a plurality" of "one or more" as described herein means "two or more".
The pressure in the present invention is an absolute pressure.
The technical scheme provided by the invention has the following beneficial effects:
the method overcomes the defects of treatment or recycling application of heavy component solution containing catalyst in the prior art, and hydrolyzes isooctanoate and isooctanoic anhydride to obtain isooctanoic acid by treating the rectified heavy component containing catalyst generated in the production process of isooctanoic acid.
In the method, the organic phase (oil phase) after hydrolysis reaction can be recycled to an oxidation reaction system, so that the isooctanoic acid in the heavy component can be reused on one hand, and on the other hand, the selectivity of the isooctanoic acid is improved through the hydrolysis reaction heavy component, the recycling of the catalyst is realized, and the consumption of the isooctanoic acid and the catalyst is greatly reduced; meanwhile, the production process avoids the generation of waste liquid, and the process is environment-friendly. Meanwhile, the used water can be completely recycled, so that no waste liquid is generated, the generation amount of three wastes in the production process is greatly reduced, and the treatment cost of the three wastes is saved; on the other hand, the operation process is simple, the conditions are mild, and the equipment investment is low.
In the method, the solid super acidic catalyst is adopted to treat the heavy component solution, the equipment and the production flow are simple and easy to operate, the obtained isooctanoic acid product has high quality, the purity is over 99.7 percent, the chromaticity of platinum and cobalt is less than 10, the whole process (oxidation and separation) yield of the isooctanoic acid product is up to 99 percent, the high yield of the product is realized, and the economic benefit is very considerable.
Drawings
FIG. 1 is a schematic scanning electron microscope of catalyst D prepared in example 4 of the present invention.
FIG. 2 is a flow chart of the heavy ends solution treatment process of the embodiment of the invention.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The following is a description of the relevant methods used or possible to be used in the examples or comparative examples of the invention:
wherein, the composition analysis conditions of the gas chromatography in the following examples are as follows: agilent7890, chromatographic column SH-RTX-WAX, method: temperature programming, tail-blow flow: 30mL/min, hydrogen flow: 40mL/min, air flow: 400mL/min, the split ratio is 30: 1; temperature rising procedure: from 60 ℃ to 80 ℃ at a rate of 20 ℃/min, and then to 250 ℃ over 8min, the total program time: 23.3min, detector temperature: at 260 ℃.
The specific surface area is determined by a nitrogen adsorption determination method, the specific measurement is carried out by referring to the GB-10517 standard, and the operations of rectification, chromatographic separation and the like in the embodiment are all performed by the conventional method in the technical field, and are not described in detail.
Unless otherwise specified, the reagents used below were all analytically pure and commercially available, and the contents referred to below were all in mass%.
Examples 1 to 6 are preparation examples of solid super acidic catalysts:
example 1
Mixing 700g zirconium tetrachloride, 533g aluminum trichloride and 12.3kg water, reacting at 90 deg.C for 6h, filtering, air-drying at 110 deg.C for 2h, and calcining at 400 deg.C for 4h to obtain 770g white powder carrier with specific surface area of 150m2/g。
The obtained carrier was immersed in 15.5kg of an aqueous solution of sulfuric acid having a concentration of 0.1mol/L, and 0.778g of yttrium trichloride and 0.778g of platinum dichloride were added thereto, and the mixture was immersed at 20 ℃ for 24 hours, then filtered, air-dried at 110 ℃ for 2 hours, and calcined at 400 ℃ for 4 hours, thereby obtaining 901.1g of catalyst A.
Example 2
Mixing 570g titanium tetrachloride, 650g ferric trichloride and 12.2kg water, reacting at 95 deg.C for 4h, filtering, air drying at 110 deg.C for 2h, and calcining at 500 deg.C for 3h to obtain white powder carrier 870g with specific surface area of 120m2/g。
The obtained carrier was immersed in 17.5kg of an aqueous solution of sulfuric acid having a concentration of 0.15mol/L, and 2.2g of yttrium trichloride and 2.2g of palladium dichloride were added thereto, and the mixture was immersed at 30 ℃ for 18 hours, then filtered, air-dried at 110 ℃ for 2 hours, and calcined at 500 ℃ for 3 hours, thereby obtaining 1020.3g of catalyst B.
Example 3
Mixing 533g of aluminum trichloride, 781.5g of stannic chloride and 13.1kg of water, reacting for 2h at 100 ℃, filtering, drying for 2h by blowing at 110 ℃, and roasting for 2h at 600 ℃ to obtain 860g of white powder carrier with the specific surface area of 100m2/g。
The obtained carrier was immersed in 17.2kg of an aqueous solution of sulfuric acid having a concentration of 0.2mol/L, and 8.6g of zinc dichloride was added thereto, immersed at 40 ℃ for 12 hours, filtered, air-dried at 110 ℃ for 2 hours, and calcined at 600 ℃ for 2 hours, to obtain 1000g of catalyst C.
Example 4
Mixing 700g of zirconium tetrachloride, 533g of aluminum trichloride and 12.3kg of water, adding 616.2g of ethylene glycol, reacting for 2h at 90 ℃, filtering, drying by blowing air at 110 ℃ for 2h, and roasting at 400 ℃ for 4h to obtain 770g of white powder with a nanosheet structure, wherein the specific surface area of the white powder is 500m2/g。
The obtained carrier with the nano lamellar structure is soaked in 15.5kg of sulfuric acid aqueous solution with the concentration of 0.1mol/L, 0.778g of yttrium trichloride and 0.778g of platinum dichloride are added, the carrier is soaked for 24 hours at the temperature of 20 ℃, then the carrier is filtered, the carrier is dried by blowing at the temperature of 110 ℃ for 2 hours, and the carrier is roasted at the temperature of 400 ℃ for 4 hours, so that 901.1g of catalyst D is obtained. The scanning electron microscope of the catalyst D in example 4 is shown in figure 2, and the microscopic pore canal is in nanometer scale.
Example 5
Mixing 570g titanium tetrachloride, 650g ferric trichloride and 12.2kg water, adding 610g ethylene glycol, reacting at 95 deg.C for 4h, filtering, drying at 110 deg.C by blowing for 2h, and calcining at 500 deg.C for 3h to obtain 870g white powder with nanosheet structure and specific surface area of 400m2/g。
The obtained carrier having a nanosheet layer structure was immersed in 17.5kg of an aqueous solution of sulfuric acid having a concentration of 0.15mol/L, and 2.2g of yttrium trichloride and 2.2g of palladium dichloride were added, and after immersion at 30 ℃ for 18 hours, filtration was carried out, air-drying was carried out at 110 ℃ for 2 hours, and calcination was carried out at 500 ℃ for 3 hours, to obtain 1020.3g of catalyst E.
Example 6
533g of aluminum trichloride, 781.5g of stannic chloride and 13.1kg of water are mixed, 657g of ethylene glycol is added into the mixture, the mixture reacts for 2 hours at the temperature of 100 ℃, the mixture is filtered, the mixture is dried by air blowing at the temperature of 110 ℃ for 2 hours, and the mixture is roasted at the temperature of 600 ℃ for 2 hours to obtain 860g of white powder with a nanosheet structure, wherein the specific surface area of the white powder is 300m2/g。
The obtained carrier with the nano-sheet structure is soaked in 17.2kg of sulfuric acid aqueous solution with the concentration of 0.2mol/L, 8.6g of zinc dichloride is added, the carrier is soaked for 12 hours at the temperature of 40 ℃, then the carrier is filtered, the carrier is dried by blowing at the temperature of 110 ℃ for 2 hours, and the carrier is roasted at the temperature of 600 ℃ for 2 hours, so that 1000g of catalyst F is obtained.
In the following examples 7 to 14, the heavy component treatment was carried out by using the catalysts A to F in examples 1 to 6. The process flow is shown in figure 2.
Example 7
1) Isooctyl aldehyde (the mass content of the raw material is 99 percent) and a catalyst sodium isooctanoate are respectively and continuously added into a reaction system at the feeding speed of 130g/h and 0.65g/h (the dosage of the catalyst is 0.5 percent of the mass of the isooctyl aldehyde), the total flow rate of air is 53.3L/h (the molar ratio of aldehyde to oxygen is 2), the reaction temperature is 50 ℃, the average residence time in a reactor is 10h, and the reaction pressure (absolute pressure, the same below) is 0.1 MPa.
The reaction solution was discharged at a rate of about 145g/h, and analyzed to contain 2.41% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoic acid, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 96.58% of isooctanoic acid, 0.09% of isooctanoic anhydride, 0.36% of isooctanoic acid, and 0.44% of sodium isooctanoate as a catalyst, based on the mass of the feed. The reaction yield was 96.7%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 5kPa, the number of separation tower plates is 10, the reflux ratio is 2.5, the outflow speed of separated light components is 3.7g/h, the isooctanoic acid is 128.3g/h, the purity is 99.5%, the chroma is 6Hazen, and the heavy components are 13 g/h. The boiling point of the sodium isooctanoate (catalyst) is higher, the catalyst added in the reaction process can completely enter the heavy component, and the conversion results show that the content of the sodium isooctanoate (catalyst) is 5 percent, the content of the isooctanoic acid is 90 percent, the content of the isooctanoic acid ester is 4 percent, and the content of the isooctanoic anhydride is 1 percent.
The heavy component containing the salt is mixed with water with the weight of 20 percent (namely 2.6g/h), sodium sulfate with the dosage of 1.5 percent of water is added to continuously contact and react with the solid super acidic catalyst A in a tubular reactor, the reaction temperature is 130 ℃, the pressure is 0.5MPa, and the liquid hourly space velocity (the mass of the mixture processed by the catalyst per unit mass in unit time) is 0.017h-1. After the reaction is finished, the material is cooled to 25 ℃, oil-water separation is carried out in a layer analyzer to obtain 2.55g/h of water phase and 13.05g/h of oil phase, the content of sodium iso-octoate (catalyst) in the oil phase is calculated to be 4.98%, the content of iso-octoate anhydride is measured by analysis to be 0.24%, and the content of iso-octoate ester is measured to be 0.04%. Wherein the conversion rates of the isooctanoate and the isooctanoic anhydride are respectively 94 percent and 96 percent.
3) Feeding the oil phase material into a reaction system in the step 1) to replace a catalyst sodium isooctanoate for feeding, wherein other conditions are unchanged, the obtained reaction liquid flows out at a speed of about 157.4g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), and the separation is carried out to obtain a light component outflow speed of 4.03g/h, isooctanoic acid flow of 140g/h and a heavy component flow of 13.37 g/h; the aqueous phase can be returned to the heavies in step 2) for recycling.
With the increase of the cycle times, the chromaticity of the isooctanoic acid product is gradually increased, and the activity of the catalyst is gradually reduced; the reaction is circulated for 10 times, the chroma of the isooctanoic acid product is increased to 15Hazen, the flow rate after the heavy component reaction is 16.7g/h, the conversion rate of the isooctanoic acid ester is reduced to 28 percent, and the conversion rate of the isooctanoic acid anhydride is reduced to 22 percent. The solid acid catalyst needs to be replaced, the material is used as waste liquid to be discharged, the overall yield of the isooctanoic acid is 95.4%, and the salt-containing heavy component waste liquid accounts for 1.2% of the product quality.
Example 8
1) Isooctyl aldehyde (99 percent of the mass content of the raw material), sodium isooctanoate as a catalyst and manganese isooctanoate as a catalyst (the mass ratio is 1:1) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 3.9g/h (the catalyst dosage is 3 percent of the mass of the isooctyl aldehyde), the total air flow rate is 76.2L/h (the aldehyde-oxygen ratio is 1.4), the reaction temperature is 20 ℃, the average residence time in a reactor is 40h, and the reaction pressure (absolute pressure, the same below) is 0.3 MPa.
The obtained reaction solution flowed out at a rate of about 150g/h, and analyzed to have a light component (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same) content of 1.64%, a water content of 0.12%, an isooctanoic acid content of 95.38%, isooctanoic anhydride of 0.05%, isooctanoic ester of 0.21%, and contents of sodium isooctanoate and manganese isooctanoate as catalysts of 1.3% and 1.3%, respectively, in terms of charged mass. The reaction yield was 98.8%.
2) The reaction liquid is rectified and separated, the separation pressure is 1.5kPa, the number of separation tower plates is 25, the reflux ratio is 1, the outflow speed of separated light components is 2.67g/h, the isooctanoic acid is 134.33g/h, the purity is 99.5%, the chroma is 5Hazen, and the heavy components are 13g/h, wherein the contents of the heavy components comprising sodium isooctanoate and manganese isooctanoate which are catalysts are respectively 15% and 15% (by material feeding mass conversion, the same as the subsequent embodiment), the content of isooctanoic acid is 67%, the content of isooctanoic acid ester is 2.4%, and the content of isooctanoic anhydride is 0.6%.
The above heavy salt-containing fraction was mixed with 25% by weight (i.e. 3.25g/h) of water and 0.1% of water was addedThe potassium sulfate is continuously contacted and reacted with a solid super acidic catalyst B in a tubular reactor, the reaction temperature is 160 ℃, the pressure is 1MPa, and the liquid hourly space velocity (the mass of a mixture treated by a unit mass of the catalyst in unit time) is 0.016h-1. After the reaction is finished, the material is cooled to 30 ℃, oil-water separation is carried out in a layer analyzer to obtain 3.22g/h of water phase and 13.03g/h of oil phase, and the content of the iso-caprylic anhydride and the content of the iso-caprylic ester are analyzed and measured to be 0.03 percent and 0.17 percent respectively. Wherein the conversion rates of the isooctanoate and the isooctanoic anhydride are 93 percent and 95 percent respectively.
3) And (2) feeding the oil phase material into the reaction system in the step 1) to replace catalyst (sodium isooctanoate and manganese isooctanoate) feeding, keeping other conditions unchanged, enabling the obtained reaction liquid to flow out at a speed of about 159.13g/h, performing rectification separation under the same conditions as those in the step 2), separating to obtain a light component flow-out speed of 2.87g/h, isooctanoate 143.26g/h and a heavy component of 13g/h, and returning the water phase to the heavy component in the step 2) for recycling treatment.
With the increase of the cycle times, the chromaticity of the isooctanoic acid product is gradually increased, and the activity of the catalyst is gradually reduced; the reaction is circulated for 6 times, the chroma of the isooctanoic acid product is increased to 16Hazen, the flow rate after the heavy component reaction is 13.3g/h, the conversion rate of the isooctanoic acid ester is reduced to 2 percent, and the conversion rate of the isooctanoic acid anhydride is reduced to 2 percent. The solid acid catalyst needs to be replaced, the material is used as waste liquid to be discharged, the integral yield of the isooctanoic acid is 97.4%, and the salt-containing heavy component waste liquid accounts for 1.56% of the product quality.
Example 9
1) Isooctyl aldehyde (99 percent of the mass content of the raw material), catalysts of potassium isooctanoate and cobalt isooctanoate (the mass ratio is 1:1) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 1.95g/h (the mass of the catalyst is 1.5 percent), the total air flow rate is 106.7L/h (the aldehyde-oxygen ratio is 1), the reaction temperature is 40 ℃, the average residence time in a reactor is 15h, and the reaction pressure (absolute pressure, the same below) is 0.5 MPa.
The reaction solution was discharged at a rate of about 146g/h, and analyzed to contain 1.30% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 96.71% of isooctanoic acid, 0.11% of isooctanoic anhydride, 0.43% of isooctanoic acid ester, and 0.67% of potassium isooctanoate and cobalt isooctanoate as catalysts, respectively, in terms of the mass of the feed. The reaction yield was 97.5%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 0.5kPa, the number of separation tower plates is 30, the reflux ratio is 0.5, the outflow speed of separated light components is 2.1g/h, the isooctanoic acid content is 134.15g/h, the purity is 99.5%, the chroma is 7Hazen, and the heavy component content is 9.75g/h, wherein the contents of the heavy component, namely catalyst potassium isooctanoate and cobalt isooctanoate are respectively 10% and 10% (converted by the mass of the fed materials), the content of isooctanoic acid is 72%, the content of isooctanoate is 6.4%, and the content of isooctanoic anhydride is 1.6%.
The heavy component containing salt is mixed with water with the weight of 40 percent (namely 3.90g/h), 5 percent of lithium bisulfate is added into the mixture, and the mixture is continuously contacted and reacted with the solid super acidic catalyst C in a tubular reactor, the reaction temperature is 100 ℃, the pressure is 0.1MPa, and the liquid hourly space velocity (the mass of the mixture processed by the catalyst per unit mass in unit time) is 0.014h-1. After the reaction is finished, the material is cooled to 35 ℃, oil-water separation is carried out in a layer analyzer to obtain 2.86g/h of water phase and 9.82g/h of oil phase, and the content of the iso-caprylic anhydride and the content of the iso-caprylic ester are respectively measured by analysis to be 0.13 percent and 0.64 percent. Wherein the conversion rates of the iso-caprylic ester and the iso-caprylic anhydride are respectively 90 percent and 92 percent.
3) And (2) feeding the oil phase material into the reaction system in the step 1) to replace catalyst (potassium isooctanoate and cobalt isooctanoate) feeding, wherein other conditions are not changed, the obtained reaction liquid flows out at the speed of about 153.87g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), the separation is carried out to obtain the light component outflow speed of 2.50g/h, the isooctanoate flow speed of 141.61g/h and the heavy component flow speed of 9.75g/h, and the water phase can be returned to the heavy component in the step 2) for recycling treatment.
With the increase of the cycle times, the chromaticity of the isooctanoic acid product is gradually increased, and the activity of the catalyst is gradually reduced; the reaction is circulated for 3 times, the chroma of the isooctanoic acid product is increased to 14Hazen, the flow rate after the heavy component reaction is 10.57g/h, the conversion rate of the isooctanoic acid ester is reduced to 8 percent, and the conversion rate of the isooctanoic acid anhydride is reduced to 8 percent. The solid acid catalyst needs to be replaced, the material is used as waste liquid to be discharged, the overall yield of the isooctanoic acid is 95.6%, and the salt-containing heavy component waste liquid accounts for 2.53% of the product quality.
Example 10
1) Isooctyl aldehyde (the mass content of the raw material is 99 percent) and a catalyst sodium isooctanoate are respectively and continuously added into a reaction system at the feeding speed of 130g/h and 0.65g/h (the dosage of the catalyst is 0.5 percent of the mass of the isooctyl aldehyde), the total flow rate of air is 53.3L/h (the molar ratio of aldehyde to oxygen is 2), the reaction temperature is 50 ℃, the average residence time in a reactor is 10h, and the reaction pressure (absolute pressure, the same below) is 0.1 MPa.
The reaction solution was discharged at a rate of about 145g/h, and analyzed to contain 2.41% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoic acid, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 96.58% of isooctanoic acid, 0.09% of isooctanoic anhydride, 0.36% of isooctanoic acid, and 0.45% of sodium isooctanoate as a catalyst, based on the mass of the feed. The reaction yield was 96.7%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 5kPa, the number of separation tower plates is 10, the reflux ratio is 2.5, the outflow speed of separated light components is 3.7g/h, the isooctanoic acid content is 128.3g/h, the purity is 99.5%, the chroma is 6Hazen, and the heavy components are 13g/h, wherein the heavy components comprise 5% of sodium isooctanoate (catalyst), 90% of isooctanoic acid, 4% of isooctanoate and 1% of isooctanoic anhydride.
The heavy component containing the salt is mixed with water with the weight of 20 percent (namely 2.6g/h), sodium sulfate with the dosage of 1.5 percent of water is added to continuously contact and react with the solid super acidic catalyst D in a tubular reactor, the reaction temperature is 130 ℃, the pressure is 0.5MPa, and the liquid hourly space velocity (the mass of the mixture processed by the catalyst per unit mass in unit time) is 0.017h-1. After the reaction is finished, the materials are cooled to 25 ℃, and oil-water separation is carried out in a layer analyzer to obtain 2.55g/h of water phase, 13.05g/h of oil phase, 0.04% of water content in the oil phase, 4.98% of sodium isooctanoate (catalyst), 92.48% of isooctanoate, 0.48% of octanol and 2.02% of heptanol. Wherein the conversion rate of the isooctanoic acid ester and the isooctanoic anhydride reaches 100 percent.
3) The oil phase material is sent into a reaction system in the step 1) to replace the feeding of a catalyst sodium isooctanoate, other conditions are not changed, the obtained reaction liquid flows out at the speed of about 157.4g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), the separation speed is 4.03g/h to obtain light components, the flow speed of isooctanoic acid is 140.37g/h, the flow speed of heavy components is 13g/h, the circulation is performed for 100 times, the content of isooctanoic acid products obtained by rectification is 99.5 percent, the chroma is not more than 10Hazen, the overall yield of isooctanoic acid is improved to 96.4 percent, no waste liquid containing catalyst heavy components is generated, and the catalyst consumption after the circulation is almost 0. The aqueous phase can be returned to the heavies in step 2) for recycling.
Example 11
1) Isooctyl aldehyde (99 percent of the mass content of the raw material), sodium isooctanoate as a catalyst and manganese isooctanoate as a catalyst (the mass ratio is 1:1) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 6.5g/h (the mass of the catalyst is 5 percent of that of the isooctyl aldehyde), the total air flow rate is 59.3L/h (the aldehyde-oxygen ratio is 1.8), the reaction temperature is 10 ℃, the average residence time in a reactor is 50h, and the reaction pressure (absolute pressure, the same below) is 0.1 MPa.
The obtained reaction solution flowed out at a rate of about 153g/h, and analyzed to contain 1.55% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 93.98% of isooctanoic acid, 0.02% of isooctanoic anhydride, 0.08% of isooctanoic ester, and 2.125% of sodium isooctanoate and manganese isooctanoate as catalysts, respectively, in terms of the mass of the feed. The reaction yield was 99.3%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 3.5kPa, the number of separation tower plates is 15, the reflux ratio is 2, the outflow speed of separated light components is 2.57g/h, the isooctanoic acid content is 134.18g/h, the purity is 99.5%, the chroma is 6Hazen, and the heavy components are 16.25g/h, wherein the heavy components comprise 40% of catalyst content (sodium isooctanoate and manganese isooctanoate), 59% of isooctanoic acid content, 0.8% of isooctanoate and 0.2% of isooctanoic anhydride.
The heavy component containing salt is mixed with 15 percent (namely 2.44g/h) of water by weight, and sodium sulfate with the dosage of 2 percent of water is added to continuously contact and react with the solid super acidic catalyst D in a tubular reactor, the reaction temperature is 120 ℃, the pressure is 0.3MPa, and the liquid hourly space velocity (the mass of the mixture processed by the catalyst per unit mass in unit time) is 0.02h-1. After the reaction is finished, the materials are cooled to 30 ℃, oil-water separation is carried out in a layer analyzer to obtain 2.43g/h of water phase and 16.26g/h of oil phase, wherein the water content is 0.003 percent, the contents of the catalyst sodium isooctanoate and manganese isooctanoate are respectively 19.9 percent and 19.9 percent, and the isooctanoic acid is prepared from sodium isooctanoate and manganese isooctanoateThe content of octanoic acid is 59.52%, the content of octanol is 0.10%, and the content of heptanol is 0.41%. Wherein the conversion rate of the isooctanoic acid ester and the isooctanoic anhydride reaches 100 percent.
3) Feeding the oil phase material into a reaction system in the step 1) to replace catalyst (sodium isooctanoate and manganese isooctanoate) feeding, wherein other conditions are not changed, the obtained reaction liquid flows out at a speed of about 162.76g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), the separation is carried out to obtain a light component outflow speed of 2.66g/h, isooctanoate of 143.86g/h and heavy component of 16.25g/h, the circulation is carried out for 100 times, the content of isooctanoate products obtained by rectification is 99.5 percent, the chroma is not more than 10Hazen, the integral yield of isooctanoate is improved to 97.5 percent, no waste liquid containing catalyst heavy component exists, and the catalyst consumption after the circulation is almost 0.
Example 12
1) Isooctyl aldehyde (99 percent of the mass content of the raw material), catalysts of potassium isooctanoate and cobalt isooctanoate (1: 1 of the mass ratio) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 1.3g/h (the mass of the catalyst is 1 percent of that of the isooctyl aldehyde), the total air flow rate is 66.7L/h (the aldehyde-oxygen ratio is 1.6), the reaction temperature is 30 ℃, the average residence time in a reactor is 30h, and the reaction pressure (absolute pressure, the same below) is 0.1 MPa.
The reaction solution thus obtained flowed out at a rate of about 147g/h, and was analyzed to contain 1.47% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 96.64% of isooctanoic acid, 0.18% of isooctanoic anhydride, 0.71% of isooctanoate, and 0.88% of a catalyst (potassium isooctanoate and cobalt isooctanoate). The reaction yield was 98.1%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 2.5kPa, the number of separation trays is 20, the reflux ratio is 1.5, the outflow speed of separated light components is 2.36g/h, the isooctanoic acid is 131.64g/h, the purity is 99.5%, the chroma is 7Hazen, and the heavy components are 13g/h, wherein the contents of the heavy components, namely the catalyst potassium isooctanoate and the catalyst cobalt isooctanoate, are respectively 5% and 5% (by weight), the content of the isooctanoic acid is 80%, the content of the isooctanoate is 8%, and the content of the isooctanoic anhydride is 2%.
The salt-containing heavy component was mixed with 10% by weight (i.e. 1.3g/h) of water and 1% by weight of sodium sulphate was added in the tubular reactorContinuously contact with a solid super acidic catalyst D for reaction at 140 ℃, 0.8MPa of pressure and 0.016h of liquid hourly space velocity (mass of mixture treated by unit mass of catalyst in unit time)-1. After the reaction is finished, the materials are cooled to 35 ℃, oil-water separation is carried out in a layer analyzer to obtain 1.21g/h of water phase and 13.09g/h of oil phase, wherein the water content is 0.01 percent, the catalyst content is 9.93 percent (potassium isooctanoate and cobalt isooctanoate), the isooctanoic acid content is 85.08 percent, the octanol content is 0.95 percent, and the heptanol content is 4.03 percent. Wherein the conversion rate of the isooctanoic acid ester and the isooctanoic anhydride reaches 100 percent.
3) And (2) feeding the oil phase material into the reaction system in the step 1) to replace catalyst (potassium isooctanoate and cobalt isooctanoate) feeding, wherein other conditions are not changed, the obtained reaction liquid flows out at the speed of about 158.79g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), so that the light component outflow speed is 3.03g/h, the isooctanoate is 142.77g/h, the heavy component is 13g/h, the overall yield of the isooctanoate is improved to 98.1%, no catalyst-containing heavy component waste liquid exists, and the catalyst consumption after circulation is almost 0.
Example 13
1) Isooctyl aldehyde (99% of the raw material by mass) and catalysts of sodium isooctanoate and manganese isooctanoate (the ratio is 1:1) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 3.9g/h (the mass of the catalyst is 3% of the mass of the reaction liquid), the total air flow rate is 76.2L/h (the aldehyde-oxygen ratio is 1.4), the reaction temperature is 20 ℃, the average residence time in the reactor is 40h, and the reaction pressure (absolute pressure, the same below) is 0.3 MPa.
The obtained reaction solution flowed out at a rate of about 150g/h, and analyzed to have a light component (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same) content of 1.64%, a water content of 0.12%, an isooctanoic acid content of 95.38%, isooctanoic anhydride of 0.05%, isooctanoic ester of 0.21%, and contents of sodium isooctanoate and manganese isooctanoate as catalysts of 1.3% and 1.3%, respectively, in terms of charged mass. The reaction yield was 98.8%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 1.5kPa, the number of separation tower plates is 25, the reflux ratio is 1, the outflow speed of separated light components is 2.67g/h, the isooctanoic acid is 134.33g/h, the purity is 99.5%, the chroma is 5Hazen, and the heavy components are 13g/h, wherein the heavy components comprise 30% of catalyst (sodium isooctanoate and manganese isooctanoate), 67% of isooctanoic acid, 2.4% of isooctanoate and 0.6% of isooctanoic anhydride.
The heavy component containing salt is mixed with water with the weight of 25 percent (namely 3.25g/h), potassium sulfate with the dosage of 0.1 percent of water is added to continuously contact and react with the solid super acidic catalyst E in a tubular reactor, the reaction temperature is 160 ℃, the pressure is 1MPa, and the liquid hourly space velocity (the mass of the mixture processed by the catalyst in unit time) is 0.016h-1. After the reaction is finished, the materials are cooled to 30 ℃, oil-water separation is carried out in a layer analyzer to obtain 3.22g/h of water phase and 13.03g/h of oil phase, wherein the water content is 0.03%, the contents of the catalyst sodium iso-octoate and manganese iso-octoate are 14.97%, the content of iso-octoate is 68.54%, the content of octanol is 0.29%, and the content of heptanol is 1.22%. Wherein the conversion rate of the isooctanoic acid ester and the isooctanoic anhydride reaches 100 percent.
3) Feeding the oil phase material into a reaction system in the step 1) to replace catalyst (sodium isooctanoate and manganese isooctanoate) feeding, wherein other conditions are not changed, the obtained reaction liquid flows out at a speed of about 159.13g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), the separation is carried out to obtain a light component outflow speed of 2.87g/h, isooctanoate of 143.26g/h and heavy component of 13g/h, the circulation is carried out for 100 times, the content of the isooctanoate product obtained by rectification reaches 99.5 percent, the chroma does not exceed 10Hazen, the integral yield of the isooctanoate is improved to 98.4 percent, no waste liquid containing catalyst heavy components exists, and the catalyst consumption is almost 0 after the circulation.
Example 14
1) Isooctyl aldehyde (99 percent of the mass content of the raw material), catalysts of potassium isooctanoate and cobalt isooctanoate (the mass ratio is 1:1) are respectively and continuously added into a reaction system at the feeding speeds of 130g/h and 1.95g/h (the mass of the catalyst is 1.5 percent), the total air flow rate is 106.7L/h (the aldehyde-oxygen ratio is 1), the reaction temperature is 40 ℃, the average residence time in a reactor is 15h, and the reaction pressure (absolute pressure, the same below) is 0.5 MPa.
The reaction solution was discharged at a rate of about 146g/h, and analyzed to contain 1.30% of light components (butyraldehyde, isooctanal, 3-heptanone, 3-heptanoate, and the like having a boiling point lower than that of isooctanoic acid, hereinafter the same), 0.12% of water, 96.71% of isooctanoic acid, 0.11% of isooctanoic anhydride, 0.43% of isooctanoic acid ester, and 0.67% of potassium isooctanoate and cobalt isooctanoate as catalysts, respectively, in terms of the mass of the feed. The reaction yield was 97.5%.
2) The reaction liquid is subjected to rectification separation, the separation pressure is 0.5kPa, the number of separation tower plates is 30, the reflux ratio is 0.5, the outflow speed of separated light components is 2.1g/h, the isooctanoic acid content is 134.15g/h, the purity is 99.5%, the chroma is 5Hazen, and the heavy component content is 9.75g/h, wherein the heavy component comprises 20% of catalyst (potassium isooctanoate and cobalt isooctanoate), 72% of isooctanoic acid content, 6.4% of isooctanoate and 1.6% of isooctanoic anhydride.
The heavy component containing salt is mixed with 30 percent (2.93 g/h) of water by weight, 5 percent of lithium bisulfate is added into the heavy component to continuously contact and react with the solid super acidic catalyst F in a tubular reactor, the reaction temperature is 100 ℃, the pressure is 0.2MPa, and the liquid hourly space velocity (the mass of the mixture processed by the unit mass of the catalyst in unit time) is 0.013h-1. After the reaction is finished, the materials are cooled to 30 ℃, oil-water separation is carried out in a layer analyzer to obtain 2.86g/h of water phase and 9.82g/h of oil phase, wherein the water content is 0.11 percent, the contents of the catalyst potassium isooctanoate and cobalt isooctanoate are respectively 9.93 percent and 9.93 percent, the content of isooctanoic acid is 76.03 percent, the content of octanol is 0.76 percent, and the content of heptanol is 3.23 percent. Wherein the conversion rate of the isooctanoic acid ester and the isooctanoic anhydride reaches 100 percent.
3) Feeding the oil phase material into a reaction system in the step 1) to replace catalyst (potassium isooctanoate and cobalt isooctanoate) feeding, wherein other conditions are not changed, the obtained reaction liquid flows out at a speed of about 153.87g/h, and then is subjected to rectification separation under the same conditions as those in the step 2), the separation is carried out to obtain a light component outflow speed of 2.50g/h, the isooctanoate flows out at a speed of 141.61g/h, and the heavy component flows out at a speed of 9.75g/h, the circulation is carried out for 100 times, the content of the isooctanoate product obtained by rectification is 99.5 percent, the chroma is not more than 10Hazen, the integral yield of the isooctanoate is improved to 98.2 percent, no catalyst heavy component containing waste liquid exists, and the catalyst.
If the heavy component solutions of examples 10 to 14 were not treated, they were discharged directly as waste liquid and used in turn as comparative examples 1 to 5; the data of yield of isooctanoic acid/amount of spent salt-containing catalyst and amount of catalyst used in examples 7-14 and comparative examples 1-5 are shown in Table 1 below. In comparative examples 1 to 5, the heavy components were not recycled and the catalyst amount was the amount consumed in a single oxidation reaction.
As can be seen from Table 1, the yield of isooctanoic acid in the whole process of examples 7-14 of the present invention is significantly improved, the amount of waste liquid of the catalyst containing salt is greatly reduced, and the consumption of the catalyst after the circulation is greatly reduced, compared with comparative examples 1-5. In addition, compared with examples 7 to 9, the solid super acidic catalysts D to F used in examples 11 to 14 have better effects in hydrolysis reaction of heavy components due to the carriers having the nanosheet structure, the yield of the obtained isooctanoic acid is higher, the chromaticity of the isooctanoic acid product is not reduced in the recycling process, the amount of waste liquid of the salt-containing catalyst is not reduced, and the consumption of the oxidation reaction catalyst is further greatly reduced.
As mentioned above, in the prior art of preparing isooctanoic acid by oxidizing isooctylaldehyde, the treatment of heavy component solution containing catalyst, which is generated by separating reaction solution, has a big problem, for example, the heavy component solution can be directly used as catalyst for reuse, but the indexes such as product chromaticity and the like are reduced along with the reuse; or the catalyst is subjected to acidolysis to a water phase for separation by mixing and reacting with a strong acid aqueous solution, but the product is acidic saline wastewater, the requirement on equipment material is high, and the operation is complicated. In the method of the embodiment of the invention, the heavy component solution is mixed with water and hydrolyzed under the catalysis of super-strong solid acid to obtain an oil-water two phase, the oil phase contains isooctanoic acid generated by hydrolysis, original isooctanoic acid, metal salt of isooctanoic acid, alcohol generated by hydrolysis and trace water, and after the oil phase is used as an oxidation reaction catalyst and is reused and added into an oxidation reaction, the process effectively improves the yield of isooctanoic acid and effectively converts a byproduct isooctanoate into isooctanoic acid; the water phase also contains a trace amount of isooctanoic acid, can be recycled, does not lose the isooctanoic acid in the process, and also generates no water phase waste liquid. Wherein the metal salt of the isooctanoic acid is used as a catalyst, so that the using amount of the catalyst is greatly reduced.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (12)
1. A method for processing heavy components in an isooctanoic acid crude product is characterized in that the method mixes the heavy components in the isooctanoic acid crude product obtained by oxidizing isooctyl aldehyde with water and an alkali metal salt auxiliary agent, then the mixture is contacted with a solid super acidic catalyst for reaction, the obtained reaction product is subjected to oil-water two-phase separation, and the obtained oil phase is taken as a catalyst to be circulated to a reaction system for preparing isooctanoic acid by oxidizing isooctyl aldehyde; wherein the solid super acidic catalyst is sulfate ion acidic SO doped with metal elements4 2-/MxOyA bimetallic oxide of which MxOyThe bimetallic oxide is used as a carrier, M is selected from one or more of zirconium, aluminum, titanium, iron and tin, x is 1 or 2, and y is 2 or 3.
2. The method of claim 1, wherein the step of producing heavy components from the crude product comprises: carrying out oxidation reaction on isooctyl aldehyde and air in the presence of a metal salt catalyst to obtain an isooctanoic acid crude product, and then rectifying and separating the isooctanoic acid crude product to respectively obtain solutions of a light component, isooctanoic acid and a heavy component;
preferably, the solution of the heavy component comprises 5-40% of metal salt compound, 55-90% of isooctanoic acid and 1-10% of isooctanoate, isooctanoic anhydride and isooctanoic acid isomer by mass fraction.
3. The method according to claim 2, wherein the metal salt catalyst is a metal salt of isooctanoic acid, and the metal element is one or more selected from sodium, potassium, iron, copper, manganese, cobalt and palladium; more preferably, the metal salt catalyst is sodium isooctanoate, a mixture of sodium isooctanoate and manganese isooctanoate and/or a mixture of potassium isooctanoate and cobalt isooctanoate;
the dosage of the metal salt catalyst is 0.5-5%, preferably 1-3% of the total mass of the reaction liquid.
4. The method according to claim 1, characterized in that the amount of water mixed with the heavies is 10-40%, preferably 20-30% of the weight of the heavies solution; the alkali metal salt auxiliary agent is sulfate and/or bisulfate of alkali metal; the amount added is preferably 0.1% to 5%, more preferably 1% to 2%, by mass of the amount of water used.
5. The method according to claim 1 or 4, wherein the ratio of the mass flow rate of the mixed solution of the heavy components, water and the alkali metal salt auxiliary agent to the mass of the catalyst is 0.01h-1～0.02h-1。
6. The method of claim 1, wherein the support has a nanosheet structure; preferably, the support is selected from ZrO2-Al2O3、TiO2-Al2O3、ZrO2-Fe2O3、TiO2-SnO2、Al2O3-Fe2O3、ZrO2-TiO2、ZrO2-SnO2、Al2O3-SnO2、TiO2-Fe2O3And SnO2-Fe2O3One or more of; preferably, the doped metal element is selected from one or more of yttrium, platinum, palladium and zinc.
7. The method according to claim 6, wherein the method for preparing the carrier of the solid super acidic catalyst comprises: mixing two of zirconium tetrachloride, aluminum trichloride, titanium tetrachloride, ferric trichloride and stannic chloride with water, reacting for 2-6 h at 90-100 ℃, filtering, drying, and roasting for 2-4 h at 400-600 ℃ to obtain the carrier.
8. The method according to claim 6, wherein the method for preparing the carrier of the solid super acidic catalyst comprises: mixing two of zirconium tetrachloride, aluminum trichloride, titanium tetrachloride, ferric trichloride and stannic chloride with water, adding ethylene glycol, reacting for 2-6 h at 90-100 ℃, filtering, drying, and roasting for 2-4 h at 400-600 ℃ to obtain the carrier with the nanosheet structure.
9. The method according to claim 7 or 8, wherein the method for preparing the solid super acid catalyst comprises: soaking the obtained carrier in a sulfuric acid aqueous solution, adding one or more chlorides selected from yttrium trichloride, platinum dichloride, palladium dichloride and zinc dichloride, wherein the concentration of sulfuric acid is 0.1-0.2mol/L, the addition amount of the chlorides is 0.01-0.05% of that of the sulfuric acid aqueous solution according to mass fraction, soaking for 12-24 h at 20-40 ℃, filtering, drying, and roasting for 2-4 h at 400-600 ℃ to obtain the solid super acid catalyst.
10. The process according to any one of claims 1 to 9, wherein the temperature of the contact reaction with the solid super acid is from 100 ℃ to 160 ℃, preferably from 120 ℃ to 140 ℃; the reaction pressure is 0.1MPa-1.0MPa, preferably 0.2MPa-0.5 MPa; the retention time is 10min-120min, preferably 30min-60 min.
11. The process according to any one of claims 1 to 10, wherein the contact reaction with the solid super acidic catalyst is continuously carried out in a tubular reactor; the oil-water two-phase separation is carried out in a decanter, and the temperature is preferably 25-35 ℃.
12. Process according to any one of claims 1 to 10, characterized in that the aqueous phase is recycled to the heavy fraction of the crude isooctanoic acid.
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