CN113926446A - Renewable catalyst, preparation method and application thereof - Google Patents

Renewable catalyst, preparation method and application thereof Download PDF

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CN113926446A
CN113926446A CN202010616129.0A CN202010616129A CN113926446A CN 113926446 A CN113926446 A CN 113926446A CN 202010616129 A CN202010616129 A CN 202010616129A CN 113926446 A CN113926446 A CN 113926446A
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catalyst
regeneration
active component
renewable
cerium
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邵益
吕建刚
刘波
周海春
王迪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • 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 provides a renewable catalyst and a preparation method thereof, wherein the renewable catalyst comprises: the catalyst comprises a catalyst carrier, an active component and a regeneration auxiliary agent, wherein the active component comprises metal oxide, the regeneration auxiliary agent comprises one or more rare earth oxide, the regeneration auxiliary agent is loaded on the catalyst loaded with the active component, so that the catalyst can be helped to activate oxygen during regeneration, the combustion of carbon deposit during regeneration is promoted, the regeneration temperature of the catalyst is reduced, the reduction of the L acid content of the catalyst during high-temperature regeneration is avoided, and the regeneration activity and the service life of the catalyst are influenced.

Description

Renewable catalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a renewable catalyst, and a preparation method and application thereof.
Background
1, 3-butadiene is widely used in the chemical industry, butadiene being the main raw material for synthetic styrene-butadiene rubber (SBR), polybutadiene rubber (BR), chloroprene rubber and nitrile rubber. The largest for styrene butadiene rubber, followed by polybutadiene rubber (mainly cis-butadiene rubber). Butadiene is also used in the production of styrene-butadiene latex, ABS resin, adiponitrile, etc., which is a raw material for the production of nylon 66. At present, the byproduct C4 fraction of ethylene production by steam cracking is the main source of butadiene, and about 97 percent of the global devices adopt a cracking C4 mixture extraction process. However, the price of petroleum has increased in recent years, and the impact of global lightening of steam cracking feedstocks on butadiene production has made it important to develop alternative methods for producing butadiene.
The preparation of butadiene from ethanol mainly comprises two production methods, namely a one-step method and a two-step method: the method comprises the steps of feeding ethanol independently by a one-step method to produce butadiene by one step; two-step process ethanol is first dehydrogenated to acetaldehyde in one reactor and then converted to butadiene in another reactor starting from a mixture of ethanol and acetaldehyde. The complete reaction route for preparing butadiene from ethanol is as follows: (1) firstly, carrying out anaerobic dehydrogenation on part of ethanol to generate acetaldehyde; (2) two molecules of acetaldehyde are subjected to aldol condensation reaction to generate 3-hydroxybutyraldehyde; (3) then 3-hydroxy butyraldehyde is dehydrated and converted into 2-butenal; (4) 2-butenal and ethanol are subjected to an MPVO intermolecular hydrogen transfer reaction to be converted into 2-butenol, and the ethanol is dehydrogenated to generate acetaldehyde again; (5) finally, the 2-butenol is dehydrated to form butadiene.
(1)CH3CH2OH→CH3CHO+H2
(2)2CH3CHO→CH3-CHOH-CH2-CHO
(3)CH3-CHOH-CH2-CHO→CH3-CH＝CH-CHO+H2O
(4)CH3-CH＝CH-CHO+CH3CH2OH→CH3-CH＝CH-CH2OH+CH3CHO
(5)CH3-CH＝CH-CH2OH→CH2＝CH-CH＝CH2
In the reaction process, various side reactions exist, particularly the dehydration of ethanol to generate ethylene, ether and aldehyde polymerization reaction to generate heavy components with more than five carbons, and other reactions (such as cracking, hydrogenation, cyclization, Diels-Alder reaction and the like) can also occur.
United states Union carbide (Process Economics Program Report 35E, On-pure Butadiene production. IHS Markit, California, 2012) uses 2% Ta2O5/SiO2The catalyst has butadiene selectivity of 63% obtained by a two-step method at the temperature of 325-350 ℃, the service life of the catalyst is 120h, the catalyst is calcined by air containing nitric acid at 400 ℃ in the regeneration process, the nitric acid is needed to assist in oxidizing carbon deposition, and if the catalyst is directly calcined and regenerated at 500 ℃ without using the nitric acid, the catalyst cannot recover the original activity. Similarly, Dumeignil et al (Green chem., 2018, 20: 3203-3209) use ZnTa-TUD-1 catalyst, after a continuous reaction time of 60h, the butadiene selectivity is reduced from 73% to below 60%, after calcination and regeneration, the catalyst activity is recovered, but after 15h, the activity is reduced to the activity level before regeneration, and the reason for the problem is that the structure or properties of the surface species of the catalyst are changed after calcination.
However, in the existing catalysts for preparing butadiene, the butadiene selectivity of the tantalum system catalyst is high, but the regeneration condition of the tantalum system catalyst is harsh, the regeneration temperature is generally as high as 550 ℃, the L acid content in the regenerated catalyst is reduced, and the activity of the regenerated catalyst is reduced, so that research and development of a renewable catalyst and a regeneration method for preparing 1, 3-butadiene from ethanol are needed to overcome the problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a renewable catalyst and a regeneration method, wherein a regeneration auxiliary agent component with activated oxygen is loaded on a catalyst loaded with an active component, so that the combustion of carbon deposition during the regeneration of the catalyst is promoted, the regeneration temperature of the catalyst is reduced, the reduction of the L acid content of the catalyst due to high-temperature regeneration is avoided, the regeneration activity and the service life of the catalyst are influenced, and the obtained renewable catalyst after regeneration can still show good catalytic performance when used for preparing 1, 3-butadiene, especially for preparing 1, 3-butadiene from a mixture of ethanol and acetaldehyde.
In a first aspect, the present invention provides a regenerable catalyst comprising: catalyst carrier, active component and regeneration assistant.
According to some preferred embodiments of the invention, the active component comprises a metal oxide.
According to some preferred embodiments of the invention, the metal oxide comprises tantalum oxide and the regeneration aid comprises one or more of rare earth oxides.
According to some preferred embodiments of the invention, the metal oxide is tantalum oxide.
According to some embodiments of the invention, the regeneration aid comprises one or more of cerium oxide, lanthanum oxide.
According to some preferred embodiments of the invention, the regeneration aid is cerium oxide.
According to some specific embodiments of the present invention, the amount of the regenerated catalyst L acid before regeneration is 50 to 220 μmol/g and the amount of the regenerated catalyst L acid after regeneration is 45 to 200 μmol/g by pyridine infrared analysis, and thus it can be seen that the amount of the regenerated catalyst L acid after regeneration can be maintained at 90% or more compared with the fresh regenerated catalyst.
The inventor finds that compared with the prior art, the regeneration auxiliary agent is added to help activate oxygen during catalyst regeneration, promote the combustion of carbon deposit during regeneration, and reduce the regeneration temperature of the catalyst, so that the reduction of the L acid content of the catalyst during high-temperature regeneration can be avoided, and the regeneration activity and the service life of the catalyst are influenced.
According to some embodiments of the present invention, the catalyst support is an amorphous mesoporous silica support, preferably an amorphous mesoporous silica support having a disordered pore structure, more preferably an amorphous mesoporous silica support having a disordered pore structure with an average pore diameter of 4 to 50 nm.
In the present invention, the amorphous silica having a disordered pore structure refers to amorphous silica having a disordered mesoporous structure and a submicron pore structure formed by disordered stacking of pore channels.
According to some specific embodiments of the invention, the catalyst support comprises one or more of silica gel type a, silica gel type B, silica gel type C, or Davisil Grade 646.
According to some embodiments of the invention, the specific surface area of the catalyst support is 100-2/g。
According to a preferred embodiment of the present invention, the specific surface area of the catalyst support may be 100m2/g、200m2/g、300m2/g、350m2/g、500m2/g、660m2/g、700m2G and any value in between.
According to some embodiments of the present invention, the specific surface area of the catalyst support is 300-700m2/g。
According to some preferred embodiments of the present invention, the specific surface area of the catalyst support is 350-700m2/g。
According to some embodiments of the invention, the mass of the active component is 0.1 to 10 wt% of the mass of the catalyst support.
According to a preferred embodiment of the invention, the mass of the active component represents 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt% and any value in between, such as 0.1-0.5 wt% of the mass of the catalyst support.
According to some specific embodiments of the invention, the mass of the active component is 0.2 to 6 wt% of the mass of the catalyst support.
According to some preferred embodiments of the invention, the mass of the active component is 2-4 wt% of the mass of the catalyst support.
According to some embodiments of the invention, the mass of the regeneration aid comprises 0.1 to 3 wt% of the mass of the catalyst support.
According to a preferred embodiment of the invention, the regeneration aid constitutes 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt% and any value in between, such as 0.1-0.5 wt%, of the mass of the catalyst support.
According to some specific embodiments of the invention, the mass of the regeneration aid is 0.2 to 2 wt% of the mass of the catalyst support.
According to some preferred embodiments of the invention, the mass of the regeneration aid is 0.4 to 1.5 wt% of the mass of the catalyst support.
According to some embodiments of the invention, the mass ratio of the regeneration aid to the active component is from 1:2 to 1: 20.
The inventor finds that the addition of a small amount of regeneration auxiliary agent can regenerate and activate oxygen in the regeneration process of the catalyst, so that the regeneration temperature is reduced; however, the added regeneration aid also becomes an active site for the reaction of reactants, resulting in an increase in reaction by-products, and therefore, it is necessary to control the mass ratio of the regeneration aid to the active component to lower the regeneration temperature and reduce the side reaction products.
In a second aspect, the present invention provides a method for preparing the above-mentioned regenerable catalyst, comprising:
s1, loading an active component on a catalyst carrier to obtain an active component-loaded catalyst;
s2, in a rare earth compound solution, carrying out impregnation treatment on the catalyst loaded with the active component to obtain the renewable catalyst.
According to some embodiments of the invention, the rare earth compound comprises one or more of anhydrous rare earth acetate, rare earth nitrate, rare earth halide, rare earth carbonate.
According to some embodiments of the invention, the rare earth compound comprises one or more of cerium acetate, cerium bromide, cerium chloride, cerium carbonate, cerium nitrate, lanthanum acetate, lanthanum nitrate.
According to some preferred embodiments of the invention, the rare earth compound comprises one or more of cerium acetate, cerium nitrate, cerium chloride.
According to some embodiments of the invention, the step S1 includes:
s1a, dipping a catalyst carrier in an active component precursor solution to obtain a catalyst precursor;
s1b, drying and roasting the catalyst precursor to obtain the catalyst loaded with the active component.
In the present invention, the active component precursor is preferably a metal precursor, which is any compound containing at least the metal element and capable of releasing the metal element in a reactive form, and therefore, the metal precursor is advantageously a soluble salt of the metal.
According to some embodiments of the invention, the metal precursor is selected from one or more of soluble salts containing tantalum, preferably at least one of soluble salts containing tantalum.
According to some embodiments of the invention, the soluble salt may comprise an inorganic salt or alkoxide.
Wherein the alkoxide may be, for example, of the formula M (OR)nA compound of the structure shown wherein M is a metal element, R ═ ethylAnd (2) a methyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, and the like.
According to some specific embodiments of the invention, the inorganic salt comprises one or more of a halide, nitrate, sulfate, phosphate, hydroxide, carbonate, carboxylate, alkoxide.
According to some preferred embodiments of the invention, the inorganic salt comprises one or more of a chloride, a nitrate, a carboxylate, an alcoholate.
According to some specific embodiments of the invention, the metal precursor comprises one or more of tantalum pentaethoxide, tantalum pentachloride.
According to some embodiments of the invention, the drying process comprises a vacuum drying process and a constant temperature drying process.
According to some embodiments of the invention, the temperature of the vacuum drying process is 50-80 ℃ and the time is 1-12 h.
According to some specific embodiments of the present invention, the temperature of the constant-temperature drying treatment is 100-120 ℃ and the time is 12-24 h.
According to some embodiments of the present invention, the temperature of the baking treatment is 500-650 ℃ for 3-6 h.
In a third aspect, the present invention provides the use of a renewable catalyst as described above or a renewable catalyst prepared according to the above preparation method for the preparation of 1, 3-butadiene, in particular for the preparation of 1, 3-butadiene from ethanol.
In a fourth aspect, the present invention provides a method for preparing 1, 3-butadiene, comprising:
1) contacting the raw material with a renewable catalyst to prepare 1, 3-butadiene;
2) carrying out regeneration treatment on the deactivated renewable catalyst, and circulating the regenerated renewable catalyst to the step 1) to continuously participate in the reaction;
wherein, the renewable catalyst is the renewable catalyst or the renewable catalyst prepared by the preparation method.
According to some embodiments of the invention, the feedstock comprises at least one of ethanol, acetaldehyde.
According to some embodiments of the invention, the feedstock is a mixture of ethanol and acetaldehyde.
According to some preferred embodiments of the invention, the molar ratio of ethanol: acetaldehyde is (2-5): 1, preferably (2.5-4): 1.
according to a preferred embodiment of the invention, the ethanol to acetaldehyde molar ratio may be (2: 1), (2.5: 1), (3: 1), (3.5: 1), (4: 1), (4.5: 1), (5: 1) and any value in between, for example (2-2.5): 1.
according to some specific embodiments of the invention, the feedstock further comprises water.
According to some specific embodiments of the invention, the water is present in an amount of 5-50% by mass of the total feedstock.
According to a preferred embodiment of the invention, the mass of water may represent 10%, 15%, 20%, 25%, 30%, 35%, 40% and 45% and any value in between, preferably 8-30% of the mass of the total raw material.
According to some specific embodiments of the invention, the contacting conditions comprise: the space velocity of the raw material is 0.5h-1-5h-1。
According to a preferred embodiment of the present invention, the space velocity of the feed solution may be 0.8h-1、1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1、4.5h-1And any value in between, preferably 0.8-3h-1。
According to some embodiments of the invention, the reaction temperature is from 300 ℃ to 400 ℃.
According to a preferred embodiment of the present invention, the reaction temperature may be 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ and any value therebetween, preferably 320 ℃ to 350 ℃.
According to some embodiments of the invention, the reaction pressure is from 100kPa to 200 kPa.
According to some embodiments of the invention, the temperature of the regeneration treatment is 400-550 ℃.
According to the preferred embodiment of the present invention, the temperature of the regeneration treatment may be 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃ and any value therebetween, preferably 450-.
According to some specific embodiments of the invention, the regeneration pressure is 0.2 to 2 MPa.
According to a preferred embodiment of the present invention, the regeneration pressure may be 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa and any value therebetween, preferably 0.5-1 MPa.
According to some specific embodiments of the invention, the air flow is 10-100 mL/min.
According to a preferred embodiment of the present invention, the air flow may be 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, and any value in between, preferably 50-70 mL/min.
According to some embodiments of the invention, the regeneration time is 12 to 24 hours, preferably 12 to 18 hours.
In the present invention, the terms are defined as follows:
Figure BDA0002560575580000071
Figure BDA0002560575580000072
Figure BDA0002560575580000073
compared with the prior art, the invention provides a renewable catalyst and a method thereof, and the catalyst loaded with the active component is loaded with the regeneration auxiliary agent, so that the catalyst can be helped to activate oxygen during regeneration, promote the combustion of carbon deposit during regeneration, reduce the regeneration temperature of the catalyst, and avoid the reduction of the L acid content of the catalyst due to high-temperature regeneration, thereby influencing the regeneration activity and the service life of the catalyst. Compared with a fresh renewable catalyst, the L acid content of the regenerated renewable catalyst can be kept above 90%, and the regenerated renewable catalyst can keep good activity.
Drawings
FIG. 1 is a graph of the pyridine-infrared spectra of the fresh catalyst and the regenerated catalyst prepared in example 1 and comparative example 1.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The chemicals used in the examples of the present invention are all commercially available unless otherwise specified.
The detection method related in the specific embodiment of the invention is as follows:
1. the infrared spectrum is tested by an American Nicolet Nexus 670 infrared spectrometer;
2. the product on-line analysis was tested by agilent 7890A gas chromatography.
[ example 1 ]
10g of the catalyst carrier was placed in a beaker, and anhydrous ethanol was added dropwise to the beaker while stirring until the surface of the carrier was observed to be wet, and the weight of the added anhydrous ethanol was weighed to 7g, that is, 7g of anhydrous ethanol was absorbed by 10g C type silica gel.
0.972g of tantalum pentachloride are dissolved in 21g of absolute ethanol (the mass of absolute ethanol is the ratio of the mass of ethanol absorbed by the support measured aboveExample conversion, i.e. carrier mass 0.7). Placing 30g of silica carrier in a beaker, quickly dropwise adding the precursor solution into the beaker under the stirring condition, mixing with the silica carrier, sealing and standing for 2 hours, drying in a vacuum drying oven at 50 ℃ for 1 hour, and drying in a forced air drying oven at 120 ℃ for 24 hours. Finally, the dried solid is put into a muffle furnace to be roasted in the air atmosphere at the roasting temperature of 500 ℃ for 5 hours to obtain 2 percent Ta2O5/SiO2A catalyst.
0.302g of cerium nitrate was dissolved in 30g of deionized water, and 30g of 2% Ta2O5/SiO2The catalyst is placed in a beaker, and the cerium nitrate solution is quickly and dropwise added into the beaker together with 2 percent of Ta under the stirring condition2O5/SiO2And (4) mixing the catalysts. Then, the solid was allowed to stand for 12 hours, and then dried in a 120 ℃ forced air drying oven for 12 hours, and finally the dried solid was calcined in a muffle furnace at 500 ℃ to obtain 0.4% CeO2/2％Ta2O5/SiO2The catalyst can be regenerated.
[ example 2 ]
The preparation of the regenerable catalyst was the same as in example 1 except that 3% Ta was supported on the silica support2O5，1％CeO2。
[ example 3 ]
The preparation of the regenerable catalyst was the same as in example 1 except that 4% Ta was supported on the silica support2O5，1.5％CeO2。
[ example 4 ]
The preparation of the regenerable catalyst was the same as in example 1 except that 4% Ta was supported on the silica support2O5，2％CeO2。
Comparative example 1
The catalyst was prepared as in example 1, except that no CeO was supported2。
Comparative example 2
Catalyst and process for preparing sameThe preparation process of (1) is the same as that of example 1 except that Ta is not supported2O5。
Comparative example 3
The catalyst was prepared as in example 1, except that 2% Ta was supported on the silica carrier2O5，2％CeO2。
Comparative example 4
The catalyst was prepared as in example 1, except that 2.5% Ta was supported on the silica carrier2O5，0.1％CeO2。
Description of catalyst Performance testing
The reactor used in the following examples is a fixed bed reactor, the temperature of the reactor is controlled using a tube furnace with three heating zones, liquid feed is carried out using a double ram pump, and the product formed during the reaction is kept in the gas phase, so that the product can be analyzed on-line using gas chromatography to identify the product formed and the content as accurately as possible. Specific operating conditions are described in the following application examples.
[ application example 1 ]
In the following catalyst activity test, the feed had an ethanol/acetaldehyde molar ratio of 3.5:1, a water content of 10 wt%, a reaction temperature of 325 ℃, a pressure of normal pressure, and a feed flow rate of 1g/g catalyst/h WHSV based on the total mass of ethanol and acetaldehyde. The overall conversion of ethanol and acetaldehyde and the carbon selectivity of butadiene were measured at this process condition.
The catalyst regeneration conditions are as follows: the regeneration temperature is 500 ℃, the regeneration pressure is 0.5MPa, the air flow is 50mL/min, the duration is 12 hours, and the activity comparison before and after the catalyst regeneration is shown in Table 1.
TABLE 1
Figure BDA0002560575580000091
Figure BDA0002560575580000101
It can be seen from table 1 that example 1 compared to comparative example 1, the activity of the regenerated catalyst of example 1 was almost completely restored. The conversion rate of the fresh catalyst in the comparative example 1 is 34% in 15h, after the regeneration at 500 ℃, the conversion rate is only 26%, the complete recovery is not realized, and the carbon deposition on the catalyst is not completely burnt out through thermogravimetric analysis; the catalyst in the comparative example 1 is regenerated at 550 ℃ to completely remove carbon deposition, but the activity is still not completely recovered, and the conversion rate and the selectivity after 15h are respectively 29% and 76%, because the roasting temperature is too high, the L acid acidic position of the active component is damaged; example 1 comparison with comparative example 2, 0.4% CeO2/SiO2The activity of butadiene preparation by ethanol-acetaldehyde conversion is very poor, the conversion rate is only 10 percent, and the butadiene selectivity is only 2 percent, thereby showing that CeO2The reactivity itself is poor; example 1 in comparison with comparative example 3, comparative example 3 added too much cerium oxide, not only reduced the conversion, but also greatly increased the polymerization product above C5, thereby reducing the selectivity to butadiene.
Meanwhile, as can be seen from fig. 1, the positions of the characteristic peaks of the pyridine-infrared spectra of the fresh and regenerated regenerable catalysts were not changed, indicating that the structures of the characteristic sites were not changed. 2% Ta from comparative example 1 by pyridine Infrared analysis2O5/SiO2The acid content of the catalyst L is 78 mu mol/g, and is reduced to 60 mu mol/g after regeneration; 0.4% CeO prepared in example 12/2％Ta2O5/SiO2The acid content of the renewable catalyst L is 75 mu mol/g, and 72 mu mol/g after regeneration, and compared with the fresh renewable catalyst, the acid content of the renewable catalyst L after regeneration can be kept at 95%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A regenerable catalyst comprising: the catalyst comprises a catalyst carrier, an active component and a regeneration auxiliary agent, wherein the active component comprises a metal oxide, and preferably the metal oxide comprises tantalum oxide; the regeneration auxiliary agent comprises one or more of rare earth oxides, preferably comprises one or more of cerium oxide and lanthanum oxide, and more preferably comprises cerium oxide.
2. The regenerable catalyst of claim 1, wherein the catalyst support is an amorphous mesoporous silica support, preferably an amorphous mesoporous silica support having a random pore structure, more preferably an amorphous mesoporous silica support having a random pore structure with an average pore size of 4 to 50 nm; preferably, the catalyst support comprises one or more of silica gel type a, silica gel type B, silica gel type C, and Davisil Grade 646.
3. A regenerable catalyst according to claim 1 or 2, wherein the mass of said active component is 0.1-10%, preferably 0.2-6%, more preferably 2-4% of the mass of said catalyst support.
4. A regenerable catalyst as claimed in any one of claims 1 to 3, wherein the mass of the regeneration aid comprises 0.1% to 3%, preferably 0.2% to 2%, more preferably 0.4% to 1.5% of the mass of the catalyst support;
and/or the mass ratio of the regeneration auxiliary agent to the active component is 1:2-1: 20.
5. A method of making the regenerable catalyst of any one of claims 1-4, comprising:
s1, loading an active component on a catalyst carrier to obtain an active component-loaded catalyst;
s2, in a rare earth compound solution, carrying out impregnation treatment on the catalyst loaded with the active component to obtain the renewable catalyst.
6. The method according to claim 5, wherein the rare earth compound comprises one or more of anhydrous rare earth acetate, rare earth nitrate, halogenated rare earth, and rare earth carbonate, preferably comprises one or more of cerium acetate, cerium bromide, cerium chloride, cerium carbonate, cerium nitrate, lanthanum acetate, and lanthanum nitrate, and more preferably comprises one or more of cerium acetate, cerium nitrate, and cerium chloride.
7. The production method according to claim 5 or 6, wherein the step S1 includes:
s1a, dipping a catalyst carrier in an active component precursor solution to obtain a catalyst precursor;
s1b, drying and roasting the catalyst precursor to obtain the catalyst loaded with the active component.
8. Use of a renewable catalyst according to any one of claims 1 to 4 or a renewable catalyst prepared according to the preparation process of any one of claims 5 to 7 for the preparation of 1, 3-butadiene, in particular for the preparation of 1, 3-butadiene from ethanol.
9. A method for preparing 1, 3-butadiene, comprising:
1) contacting the raw material with a renewable catalyst to prepare 1, 3-butadiene;
2) carrying out regeneration treatment on the deactivated renewable catalyst, and circulating the regenerated renewable catalyst to the step 1) to continuously participate in the reaction;
wherein the renewable catalyst is the renewable catalyst according to any one of claims 1 to 4 or the renewable catalyst prepared according to the preparation method of any one of claims 5 to 7; and/or the feedstock comprises at least one of ethanol, acetaldehyde, preferably a mixture of ethanol and acetaldehyde.
10. The method of claim 9, wherein the conditions of the contacting comprise: the space velocity of the raw material is 0.5h-1-5h-1Preferably 0.8h-1-3h-1(ii) a And/or the reaction temperature is 300-400 ℃, preferably 320-350 ℃; and/or the reaction pressure is 100kPa to 200 kPa;
and/or the temperature of the regeneration treatment is 400-500 ℃, preferably 450-500 ℃; and/or the regeneration pressure is 0.2-2MPa, preferably 0.5-1 MPa; and/or the air flow is 10-100mL/min, preferably 50-70 mL/min; and/or the regeneration time is 10-24h, preferably 12-18 h.
CN202010616129.0A 2020-06-29 2020-06-29 Renewable catalyst, preparation method and application thereof Pending CN113926446A (en)

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