CN112206803B - Catalyst for selectively hydrogenating methacrolein to generate isobutyraldehyde and preparation method thereof - Google Patents
Catalyst for selectively hydrogenating methacrolein to generate isobutyraldehyde and preparation method thereof Download PDFInfo
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- CN112206803B CN112206803B CN202011059622.3A CN202011059622A CN112206803B CN 112206803 B CN112206803 B CN 112206803B CN 202011059622 A CN202011059622 A CN 202011059622A CN 112206803 B CN112206803 B CN 112206803B
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- 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
- B01J27/24—Nitrogen compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 belongs to the technical field of synthesis of isobutyraldehyde, and particularly relates to a catalyst for selectively hydrogenating methacrolein to generate isobutyraldehyde and a preparation method thereof. The invention adopts methacrolein to produce isobutyraldehyde by selective hydrogenation under the action of catalyst, and the catalyst is Ni 3 N/SiO 2 Wherein Ni 3 N is SiO 2 40-60% of mass fraction. Is made of Ni/SiO 2 Heating to 280-350 ℃ in ammonia atmosphere for nitriding reaction for 4-10 h. The method is used for the reaction of selectively hydrogenating the methacrolein to generate the isobutyraldehyde, the conversion rate of the methacrolein reaches about 98.5 percent, and the yield of the isobutyraldehyde can reach about 92 percent. The process has the advantages of good economic benefit, low catalyst cost, simple preparation method, high activity and selectivity, good stability and potential industrial application value.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing methacrolein by using isobutene, a catalyst for generating isobutyraldehyde by selectively hydrogenating methacrolein and a preparation method thereof.
Background
In order to reduce the pollution of gasoline combustion to air, improve air quality, reduce PM2.5, protect environment, ethanol gasoline has been widely popularized nationwide, which makes the blending component methyl tertiary butyl ether of gasoline stop using. Thus, 1300 ten thousand tons/year of isobutene used to produce methyl tert-butyl ether is required to find other application routes.
The company takes isobutyraldehyde as a reaction raw material to produce dodecanol ester. At present, isobutyraldehyde is mainly prepared by formylating propylene. Since n-butyraldehyde is mainly obtained by the hydroformylation of propylene, the yield of isobutyraldehyde is low, and the conversion rate of isobutyraldehyde is low at present. The current supply of isobutyraldehyde in the market is far from meeting the demand. And precious propylene resources are consumed in a large amount by adopting the method. If isobutene is oxidized into methacrolein first and then is hydrogenated selectively to form isobutyraldehyde, a new application direction is opened up for isobutene, the consumption of propylene can be saved, and the demand of the market on isobutyraldehyde is met.
The current technology of oxidizing isobutene to methacrolein is well established, and the catalyst used is basically a molybdenum-bismuth catalyst, so that the molybdenum-bismuth catalyst is also adopted in the reaction of the present invention.
The catalyst for selectively hydrogenating methacrolein to form isobutyraldehyde is the key point of the present invention. The methacrolein has a c=c bond and a c=o bond in the molecule. In the hydrogenation of methacrolein to isobutyraldehyde, it is necessary to hydrogenate the c=c bond while retaining the c=o bond. This requires that the catalyst hydrogenation capacity not be too strong. The noble metal, ni and other catalysts commonly used in industry have strong hydrogenation capability, and the final product is isobutanol instead of isobutyraldehyde.
The invention adopts Ni with relatively weak hydrogenation capability 3 N is an active component, and in order to not reduce the reactivity of the catalyst on the premise of ensuring high selectivity to isobutyraldehyde, ni/SiO is prepared firstly 2 The precursor is then nitrided into Ni 3 N/SiO 2 The catalyst is used in the selective hydrogenation of methacrolein to form isobutyraldehyde, and has excellent selectivity to the synthesized isobutyraldehyde.
Disclosure of Invention
The invention aims to provide a catalyst for preparing isobutyraldehyde from isobutene and a preparation method thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows: a catalyst for the selective hydrogenation of methacrolein to isobutyraldehyde is provided.
The catalyst for preparing isobutyraldehyde by selectively hydrogenating methacrolein is Ni 3 N/SiO 2 Catalyst, wherein Ni 3 N/SiO 2 The catalyst may be suitably selected by heating Ni/SiO 2 And nitriding the precursor at a low temperature to obtain the precursor.
Ni of the invention 3 N/SiO 2 The catalyst synthesis method comprises the following steps:
mixing nickel chloride hexahydrate, hydrazine hydrate, naOH, glycol and ethyl orthosilicate, stirring, placing the mixture in a reaction kettle, heating to 70-100 ℃ and preserving heat for 2-4 hours, fully washing the reaction product with ethanol, and then drying in vacuum to obtain Ni/SiO 2 Then Ni/SiO is added 2 Heating to 280-350 ℃ in ammonia atmosphere, and preserving heat for 4-10 h to generate a nitriding product Ni 3 N/SiO 2 。
Further, the mole ratio of the nickel chloride hexahydrate, the hydrazine hydrate, the NaOH and the tetraethoxysilane is 1-5:20-60:0.5-1.0: 2 to 5.
As preferable: the molar ratio of the nickel chloride hexahydrate to the ethyl orthosilicate is 3:5:0.3
3Ni+NH 3 ＝Ni 3 N+3/2H 2 。
Preferably, ni is synthesized 3 N is SiO 2 When the mass fraction is 40-60% (theory), the selectivity of the catalyst to isobutyraldehyde is high, and the catalyst has higher catalytic activity.
The catalyst is used for preparing isobutyraldehyde from isobutene. The application method comprises the following steps:
selective hydrogenation of methacrolein to produce isobutyraldehyde: loading the methacrolein selective hydrogenation catalyst into a fixed bed reactor, introducing the methacrolein into the reactor, wherein the reaction temperature is 100-200 ℃, the pressure is 1-2 MPa, and the mass airspeed of the methacrolein is 1.5-2.0 h -1 The molar ratio of the methacrolein to the hydrogen is 1:1-10. The addition amount of the catalyst is 0.5-3% of the mass of the methacrolein.
The invention has the advantages that:
the invention takes the isobutene with low cost and large quantity as the raw material to prepare the raw material isobutyraldehyde required by the production of the company, the cost is lower, and the raw material is ensured. And a new comprehensive utilization way for isobutene is opened up.
The invention focuses on the selective hydrogenation of methacrolein to isobutyraldehyde. Ni used 3 Compared with noble metal catalysts used in other methods, the N catalyst has the advantages of greatly reduced cost and strong competitiveness. And, with Ni catalyst, ni 3 The N catalyst has moderate hydrogenation capability, mild reaction conditions, high stability and high selectivity to isobutyraldehyde, and avoids the generation of a large amount of saturated hydrogenation products of isobutanol. And at the same time, catalyst deactivation caused by polymerization of methacrolein is avoided.
In the catalyst of the invention, ni 3 High N content, more active centers and high reactivity. Ni in catalyst 3 N is connected with N in the surface carbon layer, interaction exists, and electrons on the nitrogen can be transferred to Ni 3 The electron cloud density of the N surface is increased, so that the activation of C=C double bonds in the methacrolein is promoted, and the reactivity is improved.
Detailed Description
The invention is further described below in connection with examples, but is not limited thereto.
Example 1
The catalyst for preparing isobutyraldehyde by selectively hydrogenating methacrolein comprises the following steps:
64g of nickel chloride hexahydrate (0.27 mole), 150mL of hydrazine hydrate (3.0 mole), 2g of NaOH (0.05 mole), 500mL of glycol and 120g of ethyl orthosilicate (0.58 mole) are taken and mixed, stirred and then placed in a reaction kettle, heated to 75 ℃ and kept for 3 hours, the reaction product is fully washed by ethanol, and then dried in vacuum to obtain Ni/SiO 2 Then Ni/SiO is added 2 Heating to 300 ℃ in ammonia atmosphere, and preserving heat for 8 hours to generate a nitriding product Ni 3 N/SiO 2 . Wherein Ni is 3 N is SiO 2 50% of mass fraction.
Example 2
The catalyst for preparing isobutyraldehyde by selectively hydrogenating methacrolein comprises the following steps:
47.5g of nickel chloride hexahydrate (0.2 mole), 200mL of hydrazine hydrate (4.0 mole), 4g of NaOH (0.1 mole), 600mL of glycol and 106g of ethyl orthosilicate (0.51 mole) were mixed, stirred and mixed and then placed in a reactionHeating to 90 ℃ in a kettle, preserving heat for 4 hours, fully washing the reaction product with ethanol, and then drying in vacuum to obtain Ni/SiO 2 Then Ni/SiO is added 2 Heating to 350 ℃ in ammonia atmosphere and preserving heat for 7h to generate a nitriding product Ni 3 N/SiO 2 . Wherein Ni is 3 N is SiO 2 40% of mass fraction.
Example 3
Mixing 63g of nickel chloride hexahydrate (0.28 mol), 250mL of hydrazine hydrate, 5g of NaOH, 500mL of ethylene glycol and 106g of tetraethoxysilane (0.51 mol), stirring and mixing, placing into a reaction kettle, heating to 70-100 ℃ and preserving heat for 2-4 h, fully washing the reaction product with ethanol, and drying in vacuum to obtain Ni/SiO 2 Then Ni/SiO is added 2 Heating to 280-350 ℃ in ammonia atmosphere, and preserving heat for 4-10 h to generate a nitriding product Ni 3 N/SiO 2 . Wherein Ni is 3 N is SiO 2 60% of mass fraction.
The catalysts prepared in examples 1-3 were used in the selective hydrogenation of methacrolein to prepare isobutyraldehyde: loading a methacrolein selective hydrogenation catalyst into a fixed bed reactor, wherein the catalyst addition amount is 1.5% of the methacrolein mass, introducing the methacrolein into the reactor, reacting at 100 ℃ under 1MPa, and the molar ratio of the methacrolein to the hydrogen is 1:5, and obtaining the isobutyraldehyde through gas-liquid separation.
Example 4
Example 4 is mainly compared with example 1 in that: the reaction conditions are different, and specifically: selective hydrogenation of methacrolein to produce isobutyraldehyde: loading a methacrolein selective hydrogenation catalyst into a fixed bed reactor, wherein the catalyst addition amount is 2.0% of the mass of the methacrolein, introducing the methacrolein into the reactor, reacting at 120 ℃ under the pressure of 1.5MPa, and the molar ratio of the methacrolein to the hydrogen is 1:7, and obtaining the isobutyraldehyde through gas-liquid separation.
Comparative example 1
Comparative example 1 is different from example 1 in that: ni prepared 3 N/SiO 2 In Ni 3 N is SiO 2 20% of mass fraction. Other operations and implementationsExample 1 is the same.
The catalytic application was the same as in example 1.
Comparative example 2
Comparative example 2 is different from example 1 in that: ni prepared 3 N/SiO 2 In Ni 3 N is SiO 2 70% of mass fraction. The other operations were the same as in example 1.
The catalytic application was the same as in example 1.
Comparative example 3
Comparative example 3 is different from example 1 in that: the Ni/SiO is prepared without nitriding reaction 2 The catalyst was otherwise identical to that of example 1.
Comparative example 4
Comparative example 4 is different from example 1 in that: the catalyst was the same as in example 1, the catalytic reaction temperature was 200℃when the catalyst was used, and the other operations were the same as in example 1.
The catalytic application was the same as in example 1.
The reaction data in examples and comparative examples were analyzed and the results are shown in table 1:
TABLE 1 comparison of propylene conversion and isobutyraldehyde selectivity in examples and comparative examples
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified. The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the invention, but all modifications of the foregoing embodiments according to the technical principles of the present invention are included in the scope of the present invention.
Claims (4)
1. An application of a catalyst in preparing isobutyraldehyde by hydrogenation of methacrolein is characterized in that,
selective hydrogenation of methacrolein to produce isobutyraldehyde: catalyst Ni for selectively hydrogenating methylacrolein 3 N/SiO 2 Loading the mixture into a fixed bed reactor, introducing methacrolein into the reactor, reacting at 100-200 ℃ and at 1-2 MPa, wherein the molar ratio of the methacrolein to the hydrogen is 1:1-1:10, and collecting the mixture after the reaction to obtain isobutyraldehyde;
the catalyst is Ni 3 N/SiO 2 Catalyst, wherein Ni is synthesized 3 N is SiO 2 40-60% of mass fraction;
Ni 3 N/SiO 2 the preparation method of the catalyst comprises the following steps:
mixing nickel chloride hexahydrate, hydrazine hydrate, naOH, glycol and ethyl orthosilicate, stirring and mixing, placing in a reaction kettle, heating to 70-100 ℃ and preserving heat for 2-4 hours, fully washing a reaction product with ethanol, and then drying in vacuum to obtain Ni/SiO 2 Then Ni/SiO is added 2 Heating to 280-350 ℃ in an ammonia atmosphere, preserving heat for 4-10 h, and generating Ni for selectively hydrogenating methacrolein to generate isobutyraldehyde after nitridation reaction 3 N/SiO 2 A catalyst.
2. The application of the catalyst in the preparation of isobutyraldehyde by hydrogenation of methacrolein according to claim 1, wherein the molar ratio of nickel chloride hexahydrate, hydrazine hydrate, naOH and ethyl orthosilicate is 1-5:20-60:0.4-1.0: 2-7.
3. The use of the catalyst according to claim 1 for the preparation of isobutyraldehyde by hydrogenation of methacrolein, wherein Ni 3 N/SiO 2 Ni in the catalyst 3 N is SiO 2 40-60% of the mass fraction.
4. The application of the catalyst according to claim 1 in preparing isobutyraldehyde by hydrogenating methacrolein, wherein the addition amount of the catalyst is 0.5-3% of the mass of methacrolein.
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- 2020-09-30 CN CN202011059622.3A patent/CN112206803B/en active Active
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