CN105536811A - A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst - Google Patents

A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst Download PDF

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CN105536811A
CN105536811A CN201510976381.1A CN201510976381A CN105536811A CN 105536811 A CN105536811 A CN 105536811A CN 201510976381 A CN201510976381 A CN 201510976381A CN 105536811 A CN105536811 A CN 105536811A
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catalyst
core
preparation
iron
synthetic gas
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房克功
张明伟
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J23/002—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • 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
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • 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

Abstract

A core-shell type catalyst for lower-alkene preparation from synthetic gas comprises an active component and a carrier. The active component is an iron-manganese oxide with the mole ratio of Fe to Mn being 0.99-0.6:0.01-0.4. The carrier is porous silicon dioxide and covers metal components to form a core-shell structure. The mole ratio of the active component to the SiO2 is 0.15-1:0.75-0. The catalyst is advantaged by controllable product distribution, low reaction temperature, high stability and capability of effectively inhibiting secondary reactions of alkenes.

Description

A kind of core-shell catalyst of preparation of low carbon olefines by synthetic gas and method for making and application
Technical field
The present invention relates to a kind of core-shell catalyst and preparation method and application of preparation of low carbon olefines by synthetic gas.
Background technology
Low-carbon alkene (ethene, propylene and butylene) is very important organic chemical industry's basic material, has a wide range of applications.At present, the main production ways of the low-carbon alkene such as ethene, propylene produces through steam splitting process with the raw material such as naphtha, light diesel fuel, depends on petroleum resources consumingly.Along with socioeconomic development, the demand of oil and petroleum chemicals increases fast, and the scarcity of petroleum resources makes imbalance between supply and demand become increasingly conspicuous, and following energy resource structure certainly will shift.Compared with petroleum resources, coal and natural gas resource relative abundance, develop and have great importance based on the low-carbon alkene production technology of coal and natural gas.
By coal or natural gas via synthesis gas directly alkene technique functions processed come from traditional F-T synthesis, namely synthesis gas transforms and generates the very wide alkane of carbon number distribution and alkene and the organic oxygen-containing compound such as by-product alcohol aldehyde ketone acid and ester under the effect of catalyst.Because the distribution of its product is often subject to the restriction of the Anderson-Scholz-Flory regularity of distribution and the aspect such as dynamics and thermodynamics, product that is single or certain several component can not be generated, a large amount of C 5+generation serious can reduce total yield of light olefins.And because the secondary response of alkene in Primary product is as adsorbed the existence of the reaction such as secondary hydrogenation, disproportionation, isomerization of initiation again, reduce olefine selective.Therefore the synthesizing low-carbon alkene catalyst preparing high selectivity becomes the key of dealing with problems.Wherein, Si base carrier load iron is catalyst based is one of important research direction.Patent CN1083415A adopts MgO or silica-rich zeolite molecular sieve (phosphate aluminium molecular sieve) to support Iron-Manganese Catalyst, Fischer-Tropsch catalyst is improved, the low-carbon alkene of higher yields can be obtained, but catalyst preparing is complicated, reaction temperature is higher, the selective height of methane in product.CN102441383B, CN101940958B, CN102441400B, CN102441384B adopt organic compounds containing nitrogen solution, the acid solution of sugar, the mode such as cushioning liquid, hydrothermal treatment consists of ammonium salt-containing to carry out impregnation process to silica-gel carrier respectively, preparation Fe base silica gel supported synthesis gas directly prepares light olefins catalyst, to solve Fe and SiO 2the interphase interaction of carrier is strong, part Fe is difficult to be reduced, and difficulty reaches the problem of more satisfactory reactivity.But the activity stability of long-term operation is undesirable.
To sum up, the subject matter that current preparation of low carbon olefines by synthetic gas aspect exists remains: product wider distribution and complicated, comparatively unfavorable to the synthesizing low-carbon alkene of high selectivity; In F-T synthesis, temperature raises the generation being conducive to short chain light hydrocarbon in product distribution, but temperature raises and will promote side reaction, causes a large amount of carbon distribution, accelerates sintering of catalyst inactivation, and easier hydrogenation generates alkane simultaneously; The activity stability of long-term operation is undesirable.In addition, some experiments are carried out on small-sized differential reactor, and the secondary response of alkene embodies not obvious, as evaluated on integral reactor, may occur larger change.
Summary of the invention
The object of the present invention is to provide a kind of product distribute controlled, reaction temperature is lower, stability is high, can effectively suppress the hud typed synthesis gas of the iron-based of alkene secondary response directly to prepare light olefins catalyst and preparation method and application.
Along with the rise and development of nanometer technology and Green Chemistry, for realizing structure-controllable, from molecular level or nanoscale, catalyst is designed, and then the novel catalyst system exploring performance more excellent provides technical support.Design construction porous SiO of the present invention 2the catalyst with core-casing structure of coated active component FeMn.In CO hydrogenation process, catalyst with core-casing structure complex forms unique closed microenvironment, synthesis gas first could arrive to be on inner activated centre through the coated shell of outside and react, the long chain hydrocarbon generated will get rid of reaction system, also external sheath body is had to pass through, because the diffusion rate in different chain length hydrocarbon products outside shell duct is different thus realize the control of product distribution, be conducive to suppressing the again adsorption reaction of alkene on active nucleus in product simultaneously, promote the M8003 line synthesis of product.Also nano active phase sintering can be suppressed to grow up by the coated formation confinement structure of outer carrier on the other hand, improve the long period active translocation stability of catalyst.
The core-shell catalyst of preparation of low carbon olefines by synthetic gas of the present invention, its active component is iron and manganese oxides, and active component mol ratio is: Fe:Mn=(0.99-0.6): (0.01-0.4); Carrier is porous silica, is coated on metal component outer surface and forms nucleocapsid structure, active component and SiO 2mol ratio=(0.15-1): (0.75-0).
The invention provides the preparation method of the core-shell catalyst of preparation of low carbon olefines by synthetic gas, it comprises the following steps;
(1) form by catalyst, molysite, manganese salt are dissolved in ethanol, be made into the solution of total mol concentration 0.01-0.1mol/L, add polyvinylpyrrolidone again and acetic acid mix and blend makes it even, then solution is moved in polytetrafluoroethylene (PTFE) reactor, 120-200 DEG C adds thermal response 1-48h, obtains iron and manganese oxides particle suspension after reaction;
(2) in above-mentioned particle suspension, ethanol, deionized water, template is added, ammoniacal liquor adjust ph is at 8-10, silicon source reaction 8-48 hour is slowly added under the condition stirred, filtration drying, obtains the iron and manganese oxides catalyst with core-casing structure that porous silica is coated after 450-650 DEG C of roasting;
Wherein, polyvinylpyrrolidone: the mol ratio 0.1-1:1 of iron and manganese metal ion sum; The consumption volume ratio 0.1-10:100 of acetic acid and ethanol; The concentration 0.1-10g/L of iron and manganese oxides nano particle in system; The volume ratio 0.5-5/1 of alcohol and water in system.
Source of iron as above is ferric nitrate, and manganese source is manganese acetate
Template as above is softex kw, TPAOH a kind of or their mixture.
Silicon source as above is ethyl orthosilicate or MTMS, octadecyl trimethyl silane a kind of or their mixture.
The present invention also provides a kind of application of described catalyst, to it is characterized in that described catalyst, for the synthesis of gas preparing low-carbon olefins, comprising the steps:
1) reduce: at 200-400 DEG C of temperature, under 0.1-1MPa pressure, use mol ratio CO:H 2=1:(0.5-2) CO, H 2gaseous mixture or H 2gas or CO carry out reduction treatment to described catalyst, and the recovery time is 8-24h.
2), after reduction, by synthesis gas by being equipped with the reactor of described catalyst, reaction condition is: H 2the synthesis gas of/CO mol ratio=1-3; Reaction temperature is 200-360 DEG C, preferred 220-280; Pressure is 0.5-4Mpa, preferred 1-2Mpa, air speed 500-2000h -1.
The present invention compared with prior art tool has the following advantages:
Catalyst with core-casing structure remains silicon carrier wearability, acid resistance, mechanical strength advantages of higher, nucleocapsid structure is conducive to inhibit activities component sintering and grows up, improve the service life of catalysis, catalyst is easily shaped, preparation method is simple, be applicable to fixed bed, fluid bed and paste state bed reactor, be conducive to the production of catalyst, and its outer pore passage structure can Effective Regulation iron-base fischer-tropsch product distribution, change reactant and product diffusion, suppress alkene adsorb secondary response again, improve the selective of target product.Catalyst can application response process temperature low, be conducive to improving alkene selective, improve the economy of production process.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the catalyst with core-casing structure that the present invention is prepared by embodiment 1.
Fig. 2 is transmission electron microscope photo after the reduction of the catalyst with core-casing structure that the present invention is prepared by embodiment 1.
Fig. 3 is transmission electron microscope photo after the reaction of the catalyst with core-casing structure that the present invention is prepared by embodiment 1.
As can see from Figure 1 nano particle rule and there is obvious nucleocapsid structure, its uniform particle sizes, good dispersion.Endorse after reduction as can see from Figure 2 to shrink and form rattle nucleocapsid structure.Post catalyst reaction keeps nucleocapsid structure to stablize as can see from Figure 3.
Table 1 is the reactivity worth of the catalyst with core-casing structure that the present invention is prepared by embodiment.
Can see that from table 1 shell parameter can regulate and control product distribution, and effectively suppress the adsorption reaction again of alkene, improve olefine selective.
Table 2 is catalyst with core-casing structure reactivity worth under different application condition that the present invention is prepared by embodiment 4.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment.
1, the preparation of catalyst
Embodiment 1
By catalyst composition, by 0.909gFe (NO 3) 3.9H 2o, 0.06125gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.5mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.1g softex kw is added in above-mentioned particle suspension, add ammoniacal liquor adjust ph 9, under the condition stirred, slowly add 0.6g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, because Fe/Mn mol ratio in catalyst is 0.9:0.1, therefore catalyst can be labeled as Fe 0.9mn 0.1siO 2.
Embodiment 2
By catalyst composition, by 0.909gFe (NO 3) 3.9H 2o, 0.06125gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.5mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.2g softex kw is added in above-mentioned particle suspension, adjust ph is 9, under the condition stirred, slowly add 1.2g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, because Fe/Mn mol ratio in catalyst is 0.9:0.1, carrier S iO 2for 2 times of embodiment 1, therefore catalyst can be labeled as Fe 0.9mn 0.12SiO 2.
Embodiment 3
By catalyst composition, by 0.909gFe (NO 3) 3.9H 2o, 0.06125gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.5mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.4g softex kw is added in above-mentioned particle suspension, adjust ph is 9, under the condition stirred, slowly add 2.4g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, because Fe/Mn mol ratio in catalyst is 0.9:0.1, carrier S iO 2for 4 times of embodiment 1, therefore catalyst can be labeled as Fe 0.9mn 0.14SiO 2.
Embodiment 4
By catalyst composition, by 0.7575gFe (NO 3) 3.9H 2o, 0.153125gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.4mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.2g softex kw is added in above-mentioned particle suspension, adjust ph is 9, under the condition stirred, slowly add 1.2g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, be 0.75:0.25 because catalyst and embodiment 2 contrast Fe/Mn mol ratio, therefore catalyst can be labeled as Fe 0.75mn 0.252SiO 2.
Embodiment 5
By catalyst composition, by 0.606gFe (NO 3) 3.9H 2o, 0.245gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.3mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.2g softex kw is added in above-mentioned particle suspension, adjust ph is 9, under the condition stirred, slowly add 1.2g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, be 0.6:0.4 because catalyst and embodiment 2 contrast Fe/Mn mol ratio, therefore catalyst can be labeled as Fe 0.6mn 0.42SiO 2.
Embodiment 6
By catalyst composition, by 0.7575gFe (NO 3) 3.9H 2o, 0.153125gMnC 4h 6o 44H 2o is dissolved in 100mL ethanol, be made into the solution of total mol concentration 0.025mol/L, then add 1g polyvinylpyrrolidone and 0.4mL acetic acid and stir and make it even, then move in polytetrafluoroethylene (PTFE) reactor, be heated to 180 DEG C of reaction 24h, after reaction, obtain iron and manganese oxides particle suspension.
100ml ethanol, 100ml deionized water, 0.2g TPAOH is added in above-mentioned particle suspension, adjust ph is 9, under the condition stirred, slowly add 1.2g ethyl orthosilicate react 24 hours, filtration drying, the catalyst with core-casing structure that the coated particles of active components of porous silica is formed is obtained after 550 DEG C of roastings, be micropore because catalyst and embodiment 4 contrast shell, therefore catalyst can be labeled as Fe 0.75mn 0.252mirco-SiO 2.
Comparative example 1
Comparative catalyst FeMn (mol ratio 0.9:0.1)/SiO 2preparation: by 0.909gFe (NO 3) 3.9H 2o, 0.06125gMnC 4h 6o 44H 2o, 0.5ml acetic acid and 1g polyvinylpyrrolidone are dissolved in 100ml alcohol solvent and are uniformly mixed, and move in polytetrafluoroethylene (PTFE) reactor, are heated to 180 DEG C of reaction 24h, obtain particles of active components.
Be dissolved in by 0.2g softex kw in 200ml ethanol, 100ml deionized water, adjust ph, 9, slowly adds 0.6g ethyl orthosilicate and reacts 24 hours, filtration drying, after 550 DEG C of roastings, obtain porous silica under the condition stirred.Again particles of active components obtained above is dipped in above-mentioned porous SiO 2on, 120 DEG C dry 12h, at 550 DEG C roasting 4h Temperature fall to room temperature, the catalyst activity component of formation at porous silica outer surface, i.e. comparative catalyst Fe 0.9mn 0.1/ SiO 2.
2, the application of catalyst:
Each for the catalyst prepared according to above-described embodiment method 10g is respectively charged into fixed bed reactors flat-temperature zone.Undertaken by following applying step: (1) reduces: preferably reducing atmosphere H 2/ CO mol ratio=2-in-1 one-tenth gas, preferred reduction temperature 350 DEG C, reduces 8h under normal pressure.(2), after reduction terminates, H is passed into 2the synthesis gas of/CO mol ratio=2, regulation bed stressor layer, to 2.0MPa, regulates air speed to 1000h -1, be warming up to 260 DEG C, every 24 hours sample analysis.The reactivity worth of the catalyst with core-casing structure obtained by the embodiment of the present invention lists in table 1.
The catalyst 10g prepared according to embodiment 4 method is loaded fixed bed reactors flat-temperature zone.Undertaken by following applying step: (1) reduces: in table 2 step (1) exemplified application reduction temperature, pressure, atmosphere, under the recovery time, reduction treatment is carried out to described catalyst.(2) after reduction, by synthesis gas by being equipped with the reactor of described catalyst, reaction condition for carrying out reactivity worth test under the exemplified application response temperature of table 2 step (2), pressure, atmosphere, air speed.Every 24 hours sample analysis.The reactivity worth of embodiment 4 catalyst obtained by catalyst application condition of the present invention lists in table 2.
The reactivity worth of the catalyst with core-casing structure that table 1. obtains by the embodiment of the present invention.
The reactivity worth of table 2. embodiment 4 catalyst under different invention application conditions.

Claims (6)

1. a core-shell catalyst for preparation of low carbon olefines by synthetic gas, is characterized in that catalyst comprises active component and carrier, and its active component is iron and manganese oxides, and active component mol ratio is: Fe:Mn=0.99-0.6:0.01-0.4; Carrier is porous silica, is coated on metal component outer surface and forms nucleocapsid structure, active component and SiO 2mol ratio=0.15-1:0.75-0.
2. the preparation method of the core-shell catalyst of a kind of preparation of low carbon olefines by synthetic gas as claimed in claim 1, is characterized in that comprising the following steps;
(1) form by catalyst, molysite, manganese salt are dissolved in ethanol, be made into the solution of total mol concentration 0.01-0.1mol/L, add polyvinylpyrrolidone again and acetic acid mix and blend makes it even, then solution is moved in polytetrafluoroethylene (PTFE) reactor, 120-200 DEG C adds thermal response 1-48h, obtains iron and manganese oxides particle suspension after reaction;
(2) in above-mentioned particle suspension, ethanol, deionized water, template is added, ammoniacal liquor adjust ph is at 8-10, silicon source reaction 8-48 hour is slowly added under the condition stirred, filtration drying, obtains the iron and manganese oxides catalyst with core-casing structure that porous silica is coated after 450-650 DEG C of roasting;
Wherein, polyvinylpyrrolidone: the mol ratio 0.1-1:1 of iron and manganese metal ion sum; The consumption volume ratio 0.1-10:100 of acetic acid and ethanol; The concentration 0.1-10g/L of iron and manganese oxides nano particle in system; The volume ratio 0.5-5/1 of alcohol and water in system.
3. the preparation method of the core-shell catalyst of a kind of preparation of low carbon olefines by synthetic gas as claimed in claim 1, it is characterized in that described source of iron is ferric nitrate, manganese source is manganese acetate.
4. the preparation method of the core-shell catalyst of a kind of preparation of low carbon olefines by synthetic gas as claimed in claim 1, is characterized in that described template is softex kw, TPAOH a kind of or their mixture.
5. the preparation method of the core-shell catalyst of a kind of preparation of low carbon olefines by synthetic gas as claimed in claim 1, is characterized in that described silicon source is ethyl orthosilicate or MTMS, octadecyl trimethyl silane a kind of or their mixture.
6. the application of the core-shell catalyst of a kind of preparation of low carbon olefines by synthetic gas as claimed in claim 1, is characterized in that comprising the steps:
1) reduce: at 200-400 DEG C of temperature, under 0.1-1MPa pressure, use mol ratio CO:H 2cO, H of=1:0.5-2 2gaseous mixture or H 2or CO carries out reduction treatment to described catalyst, the recovery time is 8-24h;
2), after reduction, by synthesis gas by being equipped with the reactor of described catalyst, reaction condition is: H 2the synthesis gas of/CO mol ratio=1-3; Reaction temperature is 200-360 DEG C, preferred 220-280; Pressure is 0.5-4Mpa, preferred 1-2Mpa, air speed 500-2000h -1.
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CN111632608B (en) * 2019-03-01 2023-06-30 中国石化扬子石油化工有限公司 Silica supported aluminum sulfate catalyst with core-shell structure and preparation method and application thereof
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CN114950404A (en) * 2022-05-19 2022-08-30 中国科学院兰州化学物理研究所 Wear-resistant ammonia oxidation catalyst and preparation method and application thereof
CN114950404B (en) * 2022-05-19 2023-11-17 中国科学院兰州化学物理研究所 Wear-resistant ammonia oxidation catalyst and preparation method and application thereof
CN115646493A (en) * 2022-11-03 2023-01-31 包头市中君科技有限公司 Cobalt-iron bimetallic catalyst with core-shell structure and preparation method and application thereof
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