CN111718247B - Preparation method of isovaleraldehyde - Google Patents

Preparation method of isovaleraldehyde Download PDF

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CN111718247B
CN111718247B CN201910215576.2A CN201910215576A CN111718247B CN 111718247 B CN111718247 B CN 111718247B CN 201910215576 A CN201910215576 A CN 201910215576A CN 111718247 B CN111718247 B CN 111718247B
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catalyst
tower
isovaleraldehyde
absorption
liquid
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CN111718247A (en
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王中华
张永振
张德旸
刘英俊
黎源
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/783—Separation; Purification; Stabilisation; Use of additives by gas-liquid treatment, e.g. by gas-liquid absorption
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

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Abstract

The invention discloses a preparation method of isovaleraldehyde, under the action of a porous metal organic Cu catalyst, isovalerol is subjected to gas phase dehydrogenation oxidation reaction to generate isovaleraldehyde, quenching absorption separation is preferably carried out after the reaction is finished, an isovaleraldehyde product is produced by continuously separating a liquid phase, and unreacted isovalerol is recovered to continue oxidation reaction. When the catalyst is used in a process for preparing isovaleraldehyde by dehydrogenating isoamyl alcohol, the conversion rate of dehydrogenation is more than 90%, the selectivity is more than 95.0%, the catalyst is stable in the dehydrogenation process and is not easy to run off, and the stability of the catalyst is not obviously reduced after a 1500-hour life experiment. The method of the invention has simple operation and good economic benefit.

Description

Preparation method of isovaleraldehyde
Technical Field
The invention relates to a production method of isovaleraldehyde, in particular to a method for preparing isovaleraldehyde by oxidizing isoamyl alcohol, and belongs to the technical field of chemical industry.
Technical Field
Isovaleraldehyde is an important chemical raw material and is mainly applied to the fields of synthetic spices, nutritional chemicals, medicines and the like, and the existing industrialized liquid-phase oxidation method adopts catalysts such as sulfuric acid, dichromate, manganese oxide and the like, so that adverse factors such as serious corrosion to equipment, large environmental pollution, more side reactions and the like exist.
Chinese patent CN1261399C mentions a method for preparing isovaleraldehyde by using a brass catalyst to catalyze isoamylol for oxidation, wherein the brass catalyst is copper zinc or an alloy of copper nickel and copper tin, the reaction temperature is 400-500 ℃, the catalyst is easy to deposit carbon and deactivate at high temperature, and the production energy consumption is high.
Chinese patent CN106117024 mentions that the air speed is 0.8h at 800 DEG C -1 The catalyst is the mixture of amorphous silicon-aluminum, molecular sieve, alumina, boron oxide, ferric oxide, zinc oxide and zirconium oxide, and the isovaleraldehyde semi-finished product obtained by gas phase reaction also needs to be subjected to hydrogenThe sodium oxide treatment, the alumina adsorption treatment, the refining and other means have the defects of high energy consumption and complex flow, and meanwhile, the sodium hydroxide treatment of the isovaleraldehyde also has the risk of gasification and deterioration of the aldehyde under the alkali catalysis.
Chinese patent CN205868243U mentions that the method for producing isovaleraldehyde by isoamyl alcohol by using a reaction kettle has the problems of complex operation, low production efficiency and the like by using a kettle type reactor, and is not suitable for industrial large-batch continuous production.
Aiming at the defects in the process, a novel method for preparing isovaleraldehyde from isoamyl alcohol is urgently needed to be developed, and the problems of serious liquid-phase oxidation corrosion, large environmental pollution, high temperature of a gas-phase method, easy carbon deposition, high production energy consumption and the like in the existing production are solved.
Disclosure of Invention
The invention aims to provide a preparation method of isovaleraldehyde, and particularly relates to a method for preparing isovaleraldehyde by dehydrogenating and oxidizing isoamyl alcohol, which can effectively reduce the reaction operation temperature, avoid the problems of blockage of pipelines and equipment by coking organic matters and carbon deposition on the surface of a catalyst and the like caused by high temperature, and reduce energy consumption; effectively simplifies the process flow and avoids the risk of aldehyde disproportionation and deterioration in the process of using alkali to treat the isovaleraldehyde semi-finished product in the prior process or patent. The method has the advantages of simple operation, high product yield and the like, and is suitable for industrial application.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of isovaleraldehyde comprises the steps of carrying out gas-phase dehydrogenation oxidation reaction on isovalerol to generate isovaleraldehyde under the action of a porous metal organic Cu catalyst, preferably carrying out quenching absorption separation after the reaction is finished, continuously separating a liquid phase to generate an isovaleraldehyde product, and recovering unreacted isovalerol to continue carrying out oxidation reaction.
As a preferred technical scheme, the method for generating the isovaleraldehyde by the gas-phase dehydrogenation and oxidation of the isoamyl alcohol comprises the following steps: after the isoamyl alcohol is gasified, the isoamyl alcohol and carrier gas are preferably mixed with nitrogen, the mixture enters a fixed bed reactor filled with a porous metal organic Cu catalyst from the upper part, reaction liquid at the outlet of the reactor enters a quenching absorption tower for treatment, the isoamyl aldehyde product in a gas phase is absorbed by the isoamyl alcohol, the mixture of the nitrogen and the hydrogen is discharged from the top of the quenching absorption tower, and the liquid phase extracted from the bottom of the quenching absorption tower is continuously rectified to obtain the product of the isoamyl aldehyde.
In the invention, the catalyst used for the oxidation of isoamyl alcohol is a porous metal organic Cu catalyst which can be expressed as Cu-X-Y-Z, wherein X in the catalyst is one or more of Zn, Cr, Mn, Mo, Tc, W, La, Ag, Cd, Ta, Ti, Sc, V, Zr, Nb and the like, and preferably one or more of Zn, Mn, La, V and Mo.
In the invention, Y is a polycarboxyl organic matter containing N element, preferably one or more of methyl glycine diacetic acid, diethylenetriamine pentaacetic acid and hydroxyethyl ethylenediamine triacetic acid, and more preferably methyl glycine diacetic acid and/or glycine diacetic acid.
In the invention, Z is a carrier, preferably one or more of kaolin, molecular sieve, inert alumina, silicon dioxide and silica gel.
In the invention, Cu in the porous metal organic Cu catalyst exists in a valence state of 1 and 2, and preferably 1 valence; wherein the mass of Cu accounts for 25-40% of the total mass of the catalyst, the mass of X accounts for 1-15% of the total mass of the catalyst, the mass of Y accounts for 32-50% of the total mass of the catalyst, and the mass of the Z carrier accounts for 10-35% of the total mass of the catalyst. In the catalyst structure, X and Cu are both metal elements and exist in the catalyst in the form of cations, Y is a multi-carboxyl organic acid containing N, and chemical bonds and coordination bonds are formed between the carboxyl and X and Cu through lone-pair electrons on the carboxyl and N in the catalyst; cu and X, Y form a metal-organic framework material together; the carrier plays a role in dispersing the metal organic framework material, so that the activity distribution of the catalyst is more uniform, and the aggregation of active centers is avoided.
In the invention, the preparation method of the catalyst comprises the following steps: 1) preparing an aqueous solution (the concentration can be 12-24 wt%) from Cu and nitrate of metal X according to a certain proportion, adding Y into the aqueous solution, stirring for 3-6h at the temperature of 60-80 ℃, and carrying out suction filtration and drying on the obtained precipitate (preferably, the drying temperature is 80-120 ℃, and the drying time is 2-6h) to obtain the metal organic framework material; 2) and (2) mixing the metal organic framework material and the Z carrier in the step (1) according to a certain proportion, spraying and kneading the mixture by using an acidic organic aqueous solution to synthesize direct solid particles with the diameter of 2.5-3.5mm, and roasting the solid particles at the temperature of 280-350 ℃ for 4-10h to obtain the porous metal organic Cu catalyst.
In the preparation method of the catalyst, the acidic organic aqueous solution is citric acid aqueous solution, tartaric acid aqueous solution, coconut oil acid aqueous solution, lauric acid aqueous solution and the like (the concentration range is 2-10 wt%), and the acidic organic aqueous solution plays a role of a binding agent to enable the metal organic framework material to be tightly combined with the carrier.
In the invention, the reactor required by the oxidation reaction is a tower reactor or a fixed bed reactor, preferably a fixed bed reactor, and more preferably a tubular fixed bed reactor, wherein the inner diameter of the fixed bed is preferably 15-30mm, and the catalyst is filled in the reactor.
In the invention, the dehydrogenation oxidation reaction is carried out under the pressure of 0-1.0MPa, preferably 0-0.2 MPa; the temperature is 150 ℃ to 300 ℃, preferably 170 ℃ to 240 ℃; the liquid space velocity is 0.2-5.0h -1 Preferably 0.5-1.5h -1 (ii) a The space velocity of the carrier gas is 0.5-30.0h -1 Preferably 1.0 to 5.0h -1 (ii) a The carrier gas is preferably nitrogen. The pressure is gauge pressure.
In the invention, the quenching absorption adopts a tower type absorption tower, and the packing in the tower is plate type, regular packing or random packing, preferably regular packing. The absorption liquid is fed from 1/2 to 3/4, and the reaction liquid is fed from 1/8 to 1/4. The absorption liquid used for quenching and absorption is one or more of diethyl ether, methyl tert-butyl ether, dioxane, ethyl acetate, isoamyl alcohol and isovaleraldehyde, preferably isoamyl alcohol; the operation condition of the absorption tower is 0-0.1Bar, and the operation temperature is 20-40 ℃; the pressure is gauge pressure.
In the invention, the liquid phase after quenching absorption is continuously separated by a plurality of towers, preferably two towers are connected in series for operation, the top of the first tower is used for collecting isovaleraldehyde products, the tower bottom liquid of the first tower is further separated in the second tower, the isoamylol collected from the tower top is returned to the oxidation reaction part for continuous reaction, the tower bottom of the second tower is used for discharging waste liquid, the two separation towers are separated at normal pressure, and the reflux ratio is 0.5-5.
Compared with the prior art, the invention produces the isovaleraldehyde by gas phase dehydroxylation at lower operation temperature, avoids the problems of inactivation caused by easy carbon deposition on the surface of the catalyst and blockage of pipeline equipment caused by coking of organic matters due to high temperature operation in the prior art and patents, adopts the novel porous metal organic Cu catalyst, greatly improves the dispersion degree of the catalyst by introducing the carrier and the organic matters, avoids the problem of aggregation caused by poor concentration or dispersion of the catalyst in use, forms a chelate with the organic matters in the form of ions in the catalyst, has more stable structure, can form an inner hole structure with a certain aperture, increases the specific surface and mechanical strength of the catalyst, ensures the stability and higher strength of metal active components in the use process of the catalyst, thereby reducing the loss of the catalyst active components in the use process of the catalyst, the activity of the catalyst can be kept stable for a long time, so that the stability of production operation and product quality is ensured; the lone electrons on N, O in the metal organic framework are easy to form interaction with hydrogen of hydroxyl in alcohol, the reaction concentration on the surface of the catalyst is increased in the reaction process, the alcohol is promoted to be further converted into aldehyde compounds under the catalysis of Cu, and meanwhile, the acid-base synergistic effect of amino carboxylic acid serving as a chelating agent guarantees the acidity and alkalinity of the surface of the catalyst and avoids intermolecular dehydration reaction of the alcohol at high temperature; meanwhile, the activity of the active center metal ions is milder, the aldehyde is prevented from being further dehydrogenated and oxidized into ester, acid and the like, and the selectivity of the reaction is reduced. Methyl glycine diacetic acid and/or glycine diacetic acid have one amino and two carboxyl structure preferably, chelate with metal ion such as Cu and so on and form catalyst pore diameter moderate, the mechanical strength of the shaped catalyst is high, the catalyst will not appear the framework structure deformation, bed layer shrink, bed layer differential pressure rise problem with the temperature rise.
Drawings
FIG. 1 is a schematic diagram of the process for producing isovaleraldehyde from isoamyl alcohol according to the embodiment, wherein the equipment codes in the drawing are respectively: a-a fixed bed reactor, B-a quenching absorption tower, C-a product separation tower and D-isoamylol recovery tower;
the material codes in the attached drawings are respectively as follows: 1-nitrogen, 2-isoamyl alcohol, 3-recovered isoamyl alcohol, 4-discharge of a fixed bed reactor, 5-absorbent, 6-mixture of nitrogen and hydrogen, 7-quenching and absorbing the mixture, 8-heavy component, 9-isoamyl alcohol and heavy component, and 10-product.
Detailed Description
The present invention is further illustrated in detail by the following examples, but the scope of the present invention is not limited to these examples.
Gas chromatography analysis conditions of the product: agilent gas chromatograph, RTX-WAX column, keeping at 50 deg.C for 5 min; heating to 80 deg.C at 10 deg.C/min, and maintaining for 5 min; heating to 100 deg.C at 10 deg.C/min, and maintaining for 5 min; raising the temperature to 160 ℃ at a temperature of 10 ℃/min, and keeping the temperature for 15 min.
The model of the ICP analyzer is TY-9920, and the manufacturer Chongqing Ha Ke.
The sources of materials and reagents in the following examples are shown in table 1 below:
TABLE 1
Instrument and reagent Source Specification of
ICP spectrometer Chongqing Hake TY-9920 type
Gas chromatograph Agilent
Specific surface area meter Golden spectrum technology F-sorb2400
Isoamyl alcohol Is commercially available >99％
The inorganic salts used in the following examples are all commercially available unless otherwise specified.
The following examples 1-7 document the preparation of catalysts 1-7.
Measuring the strength of the catalyst; KC-3 digital display particle strength tester.
Example 1
125.5g of cuprous nitrate and 18.9g of zinc nitrate are dissolved in 1000g of distilled water to obtain a mixed salt solution, the temperature is raised to 60 ℃, 82.1g of methylglycinediacetic acid is added into the mixed salt solution under the stirring state, the temperature is maintained to be continuously stirred for 5h after the dropwise addition, the obtained solid precipitate is subjected to suction filtration, the solid precipitate is dried at 100 ℃ for 3h to obtain 152.1g of metal-organic framework material, the 152.1g of metal-organic framework material is uniformly mixed with 80g of molecular sieve, spherical particles with the diameter of 2.5-3.5mm are kneaded into by 220g of 5% citric acid aqueous solution, and the spherical particles are roasted for 5h at the temperature of 300 ℃ to obtain the catalyst 1. ICP analysis determines that the catalyst 1 comprises the following components in percentage by mass (the metal salt raw material crystal water is not counted, organic matters and carriers are not lost, citric acid is not counted, and the following components are the same as the catalyst 1 in total mass): cu27.3%, Zn2.8%, methylglycine diacetic acid 35.4%, carrier 34.5%, BET analysis catalyst 1 specific surface area 1106 (m) 2 Per g), pore volume of 0.97 (cm) 3 In terms of/g), strength 168N/mm.
Example 2
Dissolving 188.3g of cuprous nitrate and 8.9g of manganese nitrate in 1000g of distilled water to obtain a mixed salt solution, heating to 80 ℃, adding 125.9g of diethylenetriaminepentaacetic acid under the stirring state of the mixed salt solution, keeping the temperature for continuously stirring for 3 hours after the dropwise addition is finished, and pumping out the obtained solid precipitateFiltering, drying at 100 ℃ for 3h to obtain 223.9g of metal organic framework material, uniformly mixing 223.9g of metal organic framework material with 50g of molecular sieve, kneading the mixture into spherical particles with the particle size of 2.5-3.5mm by using 240g of 5% citric acid aqueous solution, and roasting the spherical particles at 320 ℃ for 5h to obtain the catalyst 2. ICP analysis determines that the catalyst 2 comprises the following components in percentage by mass of the total mass of the catalyst 2: cu34.8 percent, Mn1.0 percent, 46.0 percent of diethylenetriamine pentaacetic acid and 18.2 percent of carrier, and the specific surface area of the catalyst 2 analyzed by BET is 1078 (m) 2 Per g), pore volume of 0.95 (cm) 3 In terms of/g), strength 104N/mm.
Example 3
125.5g of cuprous nitrate and 35.3g of molybdenum nitrate are dissolved in 1000g of distilled water to obtain a mixed salt solution, the temperature is raised to 70 ℃, 120.6g of hydroxyethyl ethylenediamine triacetic acid is added under the condition that the mixed salt solution is stirred, the temperature is maintained for continuous stirring for 5h after the dropwise addition is finished, the obtained solid precipitate is subjected to suction filtration and dried for 3h at 100 ℃ to obtain 193.6g of metal organic framework material, 193.6g of metal organic framework material is uniformly mixed with 60g of molecular sieve and kneaded into spherical particles with the size of 2.5-3.5mm by 120g of 8% citric acid aqueous solution, and the spherical particles are roasted for 5h at 300 ℃ to obtain the catalyst 3. ICP analysis determines that the following components in the catalyst 3 account for the total mass of the catalyst 3 in percentage by mass: cu25.0%, Mo3.7%, 47.6% hydroxyethyl ethylenediamine triacetic acid, 23.7% support, and the BET analysis shows that the specific surface area of the catalyst 3 is 1146 (m) 2 Per g), pore volume of 0.94 (cm) 3 In terms of/g), strength 117N/mm.
Example 4
Dissolving 125.5g of cuprous nitrate and 68.6g of lanthanum nitrate in 1000g of distilled water to obtain a mixed salt solution, heating to 70 ℃, adding 109.4g of methylglycinediacetic acid under the stirring state of the mixed salt solution, keeping the temperature for continuously stirring for 5 hours after the dropwise addition is finished, carrying out suction filtration on the obtained solid precipitate, drying at 100 ℃ for 3 hours to obtain 200.7g of metal-organic framework material, uniformly mixing 200.7g of metal-organic framework material and 50g of silicon dioxide, kneading into spherical particles of 2.5-3.5mm by using 300g of 2% citric acid aqueous solution, and roasting the spherical particles at 300 ℃ for 5 hours to obtain the catalyst 4. Determination by ICP analysis of catalyst 4The catalyst comprises the following components in percentage by mass of the total mass of the catalyst 4: cu25.3%, La11.1%, 43.7% of methylglycine diacetic acid, 19.9% of carrier, and the specific surface area of catalyst 4 analyzed by BET is 1063 (m) 2 Per g), pore volume of 0.96 (cm) 3 G), strength 159N/mm.
Example 5
Dissolving 125.5g of cuprous nitrate and 30.0g of titanium nitrate in 1000g of distilled water to obtain a mixed salt solution, heating to 70 ℃, adding 66.6g of glycine diacetic acid under the condition of stirring the mixed salt solution, keeping the temperature for continuously stirring for 5h after dropwise addition, carrying out suction filtration on the obtained solid precipitate, drying at 100 ℃ for 3h to obtain 134.8g of metal-organic framework material, uniformly mixing 134.8g of metal-organic framework material with 50g of alumina, kneading into spherical particles of 2.5-3.5mm by using 240g of 5% citric acid aqueous solution, and roasting the spherical particles at 300 ℃ for 5h to obtain the catalyst 5. ICP analysis is carried out to determine that the following components in the catalyst 5 account for the total mass of the catalyst 5 in percentage by mass: cu34.3%, Ti2.6%, glycine diacetic acid 36.0%, carrier 27.1%, BET analysis showed that the specific surface area of catalyst 5 was 1039 (m) 2 Per g), pore volume of 0.96 (cm) 3 G), strength 153N/mm.
Example 6
Dissolving 125.5g of cuprous nitrate and 17.0g of zirconium nitrate in 1000g of distilled water to obtain a mixed salt solution, heating to 70 ℃, adding 57.1g of glycine diacetic acid under the condition of stirring the mixed salt solution, keeping the temperature for continuously stirring for 5 hours after dropwise addition, carrying out suction filtration on the obtained solid precipitate, drying at 100 ℃ for 3 hours to obtain 125.1g of metal organic framework material, uniformly mixing 125.1g of gold organic framework material with 50g of molecular sieve, kneading into spherical particles of 2.5-3.5mm by using 260g of 3% citric acid aqueous solution, and roasting the spherical particles at 300 ℃ for 5 hours to obtain the catalyst 6. ICP analysis determines that the catalyst 6 comprises the following components in percentage by mass of the total mass of the catalyst 6: cu36.3%, Zr2.6%, glycinediacetic acid 32.6%, carrier 28.5%, specific surface area of catalyst 6 analyzed by BET is 1048 (m) 2 G) pore volume of 0.95 (cm) 3 ,/g), strength 161N/mm.
Example 7
Dissolving 125.5g of cuprous nitrate, 18.9g of zinc nitrate and 8.5g of silver nitrate in 1000g of distilled water to obtain a mixed salt solution, heating to 70 ℃, adding 88.9g of methylglycinediacetic acid under the condition of stirring the mixed salt solution, keeping the temperature for continuously stirring for 5h after finishing dripping, carrying out suction filtration on the obtained solid precipitate, drying for 3h at 100 ℃ to obtain 164.3g of metal organic framework material, uniformly mixing 164.3g of gold organic framework material with 50g of molecular sieve, kneading into spherical particles with the size of 2.5-3.5mm by using 220g of 4% citric acid aqueous solution, and roasting for 5h at 300 ℃ to obtain the catalyst 7. ICP analysis is carried out to determine that the following components in the catalyst 7 account for the total mass of the catalyst 7 in percentage by mass: cu29.6 percent, Zn3.1 percent, Ag2.5 percent, methylglycinediacetic acid 41.5 percent and carrier 23.3 percent, and the specific surface area of the catalyst 7 analyzed by BET is 1063(m 2 Per g), pore volume of 0.96 (cm) 3 G), strength 153N/mm.
Example 8
Catalysts 1-7 were used to catalyze isoamyl alcohol to make isovaleraldehyde:
as shown in fig. 1, the flow describes: fresh isoamyl alcohol 2, recovered isoamyl alcohol 3 and carrier gas 1 react under the catalytic action of a catalyst in a fixed bed reactor A, a fixed bed reactor discharge 4 obtained at the outlet of the fixed bed reactor A is in countercurrent contact with an absorbent 5 (isoamyl alcohol) in a quenching absorption tower B, a mixture 6 of nitrogen and hydrogen is extracted from the top of the quenching absorption tower B, a liquid phase 7 material flow after quenching absorption extracted from the tower bottom of the quenching absorption tower B is separated by a product separation tower C, an isovaleraldehyde product 10 is extracted from the tower top of the product separation tower C, tower bottom material flow isoamyl alcohol and a heavy component 9 of the product separation tower C are further separated by an isoamyl alcohol recovery tower D, unreacted isoamyl alcohol is separated from the tower top of the isoamyl alcohol recovery tower D and returns to the fixed bed reactor A for further reaction, and a waste liquid heavy component 8 is extracted from the tower bottom of the D. Catalysts 1-7 are respectively filled in 7 fixed beds (the inner diameter is 20mm), isoamylol reacts under the conditions of the temperature, the pressure, the liquid space velocity and the carrier gas space velocity of the hydrogenation reaction shown in the table 2, and the carrier gas is nitrogen; also shown in Table 2 are the hydrogenation results under different conditions, the conversion and selectivity of isoamyl alcohol and isovaleraldehyde were obtained by gas chromatography analysis and calculation (the same below), and the loss of active ingredient was obtained by ICP analysis. The quenching absorption tower is a tower type, the filler is a loose pall ring filler, the operation pressure is 0.1Bar, the operation temperature is 30 ℃, the feeding position of the absorption liquid is 3/5 away from the tower bottom, the feeding position of the reaction liquid is 1/5 away from the tower bottom, and the reflux ratio is 2.
TABLE 2
Figure BDA0002001948060000101
Example 9
The catalyst 5 is used for long-period experiment, and the liquid volume space velocity is 1.0h at the temperature of 200 ℃ and the pressure of 0.1Mpa -1 Space velocity of carrier gas is 4.5h -1 The reaction is carried out by hydrogenation, and the rest is carried out for 1000h continuously as in example 8, and isovaleraldehyde is obtained at the outlet of the reactor. The results measured at different run times are shown in table 3 below.
TABLE 3
Figure BDA0002001948060000111
Example 10
As shown in figure 1, the reaction liquid after 1500 runs of example 9 is used as a raw material, a structured packing M250Y is filled in a quenching absorption tower, the reaction liquid is fed at a position 1/4 away from the tower bottom, and the space velocity of the feed of the reaction liquid entering the quenching absorption tower is 1.0h -1 Spraying isoamyl alcohol at the position which is far from 2/3 of the tower kettle, wherein the feeding space velocity of the isoamyl alcohol entering a quenching absorption tower is 0.2h -1 The operation temperature of the quenching absorption tower is 35 ℃, and the content of organic matters in the gas phase at the top of the tower after absorption is under the condition of the operation pressure of 0.05Bar<10ppm, the main components in the tower bottom are isovaleraldehyde, isoamyl alcohol and trace heavy impurities, the isovaleraldehyde is continuously separated by two towers with the reflux ratio of 5, the purity of the isovaleraldehyde extracted from the tower top of the product separation tower is 99.92 percent, and the purity of the isoamyl alcohol recovered from the tower top of the isoamyl alcohol recovery tower is 99.87 percent.
Comparative example 1
A commercial Cu/Zn catalyst containing 45% CuO and 55% ZnO was charged into a fixed bed reactor and then treated by the method shown in Table 4The catalyst is activated, and the liquid space velocity is 1h at 280 ℃ after the activation is finished -1 The other example was conducted in the same manner as example 8 (using catalyst 5) and the fixed bed reactor used in example 8, the conversion of isoamyl alcohol was 52.4%, and the selectivity of isovaleraldehyde was 92.7%.
TABLE 4 catalyst activation Process
Operating temperature C Mass% of nitrogen gas% Hydrogen gas mass% Run time h
120 80 20 0.5
150 50 50 2
180 40 60 3
200 30 70 4
230 10 90 2
Comparative example 2
The reaction solution after 1500 operations in example 9 was not subjected to quenching treatment, and the reaction solution was subjected to gas-liquid separation in a buffer tank, wherein the content of organic matters in the gas phase was 3657ppm, and the content of the organic matters in the organic matters was 98.3% of isovaleraldehyde and 1.7% of isoamyl alcohol by gas phase analysis. It can be seen that a large amount of organic matters are carried in the waste gas nitrogen without a quenching absorption link, so that the product yield is reduced, and the smell of the waste gas is large.

Claims (18)

1. A preparation method of isovaleraldehyde is characterized by comprising the following steps: under the action of a porous metal organic Cu catalyst, carrying out gas-phase dehydrogenation oxidation reaction on isoamyl alcohol to generate isovaleraldehyde, wherein the porous metal organic Cu catalyst is represented as Cu-X-Y-Z, and X is one or more of Zn, Mn, Mo, La, Ag, Ti and Zr; y is a polycarboxyl organic matter containing N element, and Z is a carrier; the Y is one or more of methylglycine diacetic acid, glycine diacetic acid, diethylenetriamine pentaacetic acid and hydroxyethyl ethylenediamine triacetic acid; the mass of Cu accounts for 25-40% of the total mass of the catalyst, the mass of X accounts for 1-15% of the total mass of the catalyst, the mass of Y accounts for 32-50% of the total mass of the catalyst, and the mass of Z accounts for 10-35% of the total mass of the catalyst.
2. The method of claim 1, wherein: after the reaction is finished, quenching absorption separation is carried out, the liquid phase is continuously separated to produce an isovaleraldehyde product, and unreacted isoamylol is recovered to continue the oxidation reaction.
3. The method of claim 1, wherein: the valence states of Cu are 1 and 2; x is one or more of Zn, Mn, La and Mo.
4. The method of claim 3, wherein: the valence state of Cu is 1.
5. The method of claim 1, wherein: and Y is methyl glycine diacetic acid and/or glycine diacetic acid.
6. The method according to any one of claims 1-4, wherein: the Z carrier is one or more of kaolin, molecular sieve, inert alumina, silicon dioxide and silica gel.
7. The method according to any one of claims 1-4, wherein: the preparation method of the porous metal organic Cu catalyst comprises the following steps: 1) preparing an aqueous solution from Cu and nitrate of metal X, adding Y into the aqueous solution, stirring for 3-6h at the temperature of 60-80 ℃, and carrying out suction filtration and drying on the obtained precipitate to obtain a metal organic framework material; 2) and (3) mixing the metal organic framework material obtained in the step (1) with a z carrier, spraying and kneading an acidic organic matter aqueous solution to synthesize solid particles, and roasting the solid particles to obtain the porous metal organic Cu catalyst.
8. The method of claim 7, wherein: the acidic organic water solution is citric acid water solution, tartaric acid water solution, coconut oil acid water solution or lauric acid water solution.
9. The method of claim 7, wherein: roasting at the temperature of 280-350 ℃ for 4-10 h.
10. The method according to any one of claims 1-4, wherein: the reactor required by the oxidation reaction is a tower reactor or a fixed bed reactor; the condition of the oxidation reaction is 0-1.0 MPa; the temperature is 150 ℃ and 300 ℃; the liquid space velocity is 0.2-5.0h -1 (ii) a The space velocity of the carrier gas is 0.5-30.0h -1 。
11. The method of claim 10, wherein: the reactor required by the oxidation reaction is a fixed bed reactor, and the pressure of the oxidation reaction is 0-0.2 MPa; the temperature is 170 ℃ and 240 ℃; the liquid space velocity is 0.5-1.5h -1 (ii) a The space velocity of the carrier gas is 1.0-5.0h -1 (ii) a The carrier gas is nitrogen.
12. The method of claim 10, wherein: the reactor required by the oxidation reaction is a tubular fixed bed reactor, and the inner diameter of the fixed bed is 15-30 mm.
13. The method according to any one of claims 1-4, wherein: the quenching absorption after the reaction is finished adopts a tower type absorption tower, and the packing in the tower is plate type, regular packing or random packing; the operation condition of the absorption tower is 0-0.1Bar, and the operation temperature is 20-40 ℃.
14. The method of claim 13, wherein: the packing in the column is structured packing.
15. The method of claim 13, wherein: the absorption liquid used for quenching and absorption is one or more of diethyl ether, methyl tert-butyl ether, dioxane, ethyl acetate, isoamyl alcohol and isovaleraldehyde; the absorption liquid is fed from 1/2 to 3/4, and the reaction liquid is fed from 1/8 to 1/4.
16. The method of claim 15, wherein: the absorption liquid used for quenching and absorption is isoamylol.
17. The method according to any one of claims 1-4, wherein: the liquid phase after quenching absorption is continuously separated by a plurality of towers.
18. The method of claim 17, wherein: the liquid phase after quenching absorption is continuously separated through the series operation of two towers, the tower top of the first tower is used for extracting isovaleraldehyde products, the tower bottom liquid of the first tower is further separated in the second tower, the isoamylol extracted from the tower top is returned to the oxidation reaction part, the tower bottom of the second tower is used for discharging waste liquid, the two separation towers are separated at normal pressure, and the reflux ratio is 0.5-5.
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