CN115106080B - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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CN115106080B
CN115106080B CN202110309382.6A CN202110309382A CN115106080B CN 115106080 B CN115106080 B CN 115106080B CN 202110309382 A CN202110309382 A CN 202110309382A CN 115106080 B CN115106080 B CN 115106080B
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CN115106080A (en
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傅怡
倪友明
朱文良
刘中民
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Dalian Institute of Chemical Physics 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
    • B01J23/16—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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • 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
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The application discloses a catalyst, a preparation method and application thereof, wherein the catalyst comprises nano ZnMnO 3 oxide and a silicon-aluminum molecular sieve; the particle size of the nano ZnMnO 3 oxide is 3-30 nm. The catalyst provided by the application is simple to prepare, mild in condition and has the characteristics of adjustable particle size, specific surface area and pore volume. Can be applied to the reaction for preparing aromatic hydrocarbon by directly converting synthesis gas, has the characteristics of high conversion rate and high aromatic hydrocarbon selectivity, and has wide application prospect.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and relates to a catalyst, a preparation method and application thereof.
Background
Aromatic hydrocarbon is an important petrochemical basic raw material, is widely applied to the preparation of three synthetic materials such as synthetic resin, synthetic rubber, synthetic fiber and the like, and has wide market demands in the production of products such as medicines, dyes, pesticides and the like. At present, aromatic hydrocarbon mainly comes from catalytic reforming of naphtha and hydrogenation of pyrolysis gasoline, and along with continuous exhaustion of petroleum resources, development of a novel non-petroleum route for preparing aromatic hydrocarbon has important research value and great strategic benefit.
The chemical synthesis gas (H 2/CO) can convert non-petroleum resources such as coal, natural gas, biomass and the like into basic petrochemical products, and has important significance in developing and taking coal as a raw material to prepare aromatic hydrocarbon through direct preparation and conversion of synthesis gas by taking the energy structure of rich coal, lean oil and less gas in China into consideration.
There are reports on the preparation of aromatic hydrocarbon by direct conversion of synthetic gas, and the bi-functional composite catalyst of oxide-molecular sieve can be used for preparing aromatic hydrocarbon with high selectivity. For example, 20 percent of CO conversion and 80 percent of aromatic hydrocarbon selectivity in hydrocarbon products can be realized on a Zn-ZrO 2 & H-ZSM-5 composite catalyst; the conversion rate of CO of 16 percent and the selectivity of aromatic hydrocarbon of 74 percent in hydrocarbon products can be realized on a ZnCrO x & H-ZSM-5 composite catalyst; the CO conversion rate of 22% and the aromatic hydrocarbon selectivity of 76% in hydrocarbon products can be realized on the Mo-ZrO 2/H-ZSM-5 composite catalyst. Although higher aromatics selectivity can be achieved using these complex catalysts, the difficulty of low CO conversion is associated. The particle size of the oxide in the composite catalyst can be reduced by a supercritical drying method, which is favorable for improving the CO conversion rate, but the method is high in price and complex in operation. The development and preparation of a simple, efficient and nano-sized catalyst, which is applied to the reaction of directly converting synthesis gas to prepare aromatic hydrocarbon, and simultaneously preparing aromatic hydrocarbon with high conversion rate and high selectivity, are still a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the problems, the application provides a catalyst, which is prepared by adjusting the preparation conditions to obtain nano ZnMnO 3 oxide with smaller particle size, then mixing the nano ZnMnO 3 oxide with a silicon-aluminum molecular sieve, and granulating. The catalyst can be used for preparing aromatic hydrocarbon by directly converting synthesis gas, and has high conversion rate, high aromatic hydrocarbon selectivity and wide application prospect. The preparation method is simple, mild in condition and strong in operability, and can be used for large-scale production.
According to one aspect of the present application, there is provided a catalyst comprising nano ZnMnO 3 oxide and a molecular sieve; the particle size of the nano ZnMnO 3 oxide is 3-30 nm.
Optionally, the upper limit of the particle size of the nano ZnMnO 3 oxide is selected from 4nm、5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm or 30nm; the lower limit is selected from 3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm or 29nm.
Optionally, the mass ratio of the nano ZnMnO 3 oxide to the silicon-aluminum molecular sieve is 1-10:1.
Optionally, the upper mass ratio limit of the nano ZnMnO 3 oxide to the aluminosilicate molecular sieve is selected from 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1; the lower limit is selected from 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1.
Optionally, the specific surface area of the nano ZnMnO 3 oxide is 50-1000 m 2/g.
Optionally, the upper limit of the specific surface area of the nano ZnMnO 3 oxide is 100m2/g、200m2/g、300m2/g、400m2/g、500m2/g、600m2/g、700m2/g、800m2/g、900m2/g or 1000m 2/g; the lower limit is selected from 50m2/g、100m2/g、200m2/g、300m2/g、400m2/g、500m2/g、600m2/g、700m2/g、800m2/g or 900m 2/g.
Optionally, the ZnMnO 3 oxide has a nanoscale porous structure.
Optionally, the pore volume of the nano ZnMnO 3 oxide is 10-300 cm 3/g.
Optionally, the upper limit of the pore volume of the nano ZnMnO 3 oxide is selected from 20cm3/g、30cm3/g、40cm3/g、50cm3/g、60cm3/g、70cm3/g、80cm3/g、90cm3/g、100cm3/g、110cm3/g、120cm3/g、130cm3/g、140cm3/g、150cm3/g、160cm3/g、170cm3/g、180cm3/g、190cm3/g、200cm3/g、210cm3/g、220cm3/g、230cm3/g、240cm3/g、250cm3/g、260cm3/g、270cm3/g、280cm3/g、290cm3/g or 300cm 3/g; the lower limit is selected from 10cm3/g、20cm3/g、30cm3/g、40cm3/g、50cm3/g、60cm3/g、70cm3/g、80cm3/g、90cm3/g、100cm3/g、110cm3/g、120cm3/g、130cm3/g、140cm3/g、150cm3/g、160cm3/g、170cm3/g、180cm3/g、190cm3/g、200cm3/g、210cm3/g、220cm3/g、230cm3/g、240cm3/g、250cm3/g、260cm3/g、270cm3/g、280cm3/g or 290cm 3/g.
Alternatively, the silica alumina molecular sieve is selected from ZSM-5 molecular sieves.
Optionally, the silica to alumina ratio of the silica to alumina molecular sieve is: siO 2/Al2O3 =140 to 260.
Optionally, the upper limit of the silica to alumina ratio (SiO 2/Al2O3) of the silica to alumina molecular sieve is selected from 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, or 260; the lower limit is selected from 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250.
According to another aspect of the present application, there is provided a method of preparing the above catalyst, the method of preparing the catalyst comprising: (1) Obtaining nano ZnMnO 3 oxide; (2) And mixing the nano ZnMnO 3 oxide with a silicon-aluminum molecular sieve to obtain the catalyst.
Optionally, the preparation method of the nano ZnMnO 3 oxide is a coprecipitation method.
Optionally, the preparation method of the nano ZnMnO 3 oxide comprises the following steps: (i) Mixing materials containing Zn source, mn source and precipitant, and reacting I to obtain an intermediate product I; (ii) And roasting the intermediate product I to obtain the nano ZnMnO 3 oxide.
Optionally, the Zn source is selected from at least one of soluble salts of zinc; the Mn source is selected from at least one of soluble salts of manganese.
Optionally, the molar ratio of Zn in the Zn source to Mn in the Mn source is 0.8-1.2:1.
Optionally, the upper limit of the molar ratio of Zn in the Zn source to Mn in the Mn source is selected from 0.9:1, 1.0:1, 1.1:1 or 1.2:1; the lower limit is selected from 0.8:1, 0.9:1, 1.0:1 or 1.1:1.
Optionally, the Zn source is selected from at least one of nitrate, acetate, chloride, sulfate of zinc; the Mn source is selected from at least one of nitrate, acetate, chloride and sulfate of manganese.
Alternatively, the temperature of reaction I is 60-80 ℃.
Alternatively, the upper temperature limit of the reaction is selected from 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the lower limit is selected from 60 ℃, 65 ℃, 70 ℃ or 75 ℃.
Optionally, in the step (i), stirring is further included; the stirring is mechanical stirring; the rotating speed of the mechanical stirring is 300-1000r/min.
Optionally, the upper rotational speed limit of the mechanical stirring is selected from 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000r/min; the lower limit is selected from 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min or 900r/min.
Optionally, the stirring time is 2-4 hours.
Optionally, the upper limit of the stirring time is selected from 2.5h, 3h, 3.5h or 4h; the lower limit is selected from 2h, 2.5h, 3h or 3.5h.
Optionally, in the step (i), further comprising adjusting pH; in the pH adjustment, the pH value after adjustment is 6-10.
Optionally, the adjusted pH upper limit is selected from 7, 8, 9 or 10; the lower limit is selected from 6, 7, 8 or 9.
Optionally, the firing conditions are: the temperature is 300-700 ℃ and the time is 3-5 h.
Optionally, the upper temperature limit of the firing is selected from 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, or 700 ℃; the lower limit is selected from 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃.
Optionally, the upper time limit of the calcination is selected from 3.5h, 4h, 4.5h or 5h; the lower limit is selected from 3h, 3.5h, 4h or 4.5h.
Specifically, the heating mode is to heat to 300-700 ℃ at a heating rate of 1-3 ℃/min, and bake for 3-5 h at the corresponding baking temperature.
Optionally, the material containing Zn source, mn source and precipitant further comprises a solvent; the solvent comprises at least one of water, ethanol and N, N-dimethylformamide.
Optionally, in said step (I), a solution a containing Zn source and Mn source and a solution B containing precipitant are mixed, reacted I to obtain intermediate I.
Optionally, the solution B containing the precipitant includes a solvent C; the solvent C is at least one selected from water, ethanol and N, N-dimethylformamide.
The concentration of the solution B containing the precipitant is 0.5-3 mol/L.
Optionally, the upper concentration limit of the precipitant is selected from 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L; the lower limit is selected from 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L or 2.5mol/L.
Optionally, the precipitant is at least one selected from ammonium carbonate and ammonium bicarbonate.
Preferably, the precipitant is selected from ammonium carbonate.
Preferably, the precipitant is selected from ammonium bicarbonate.
Optionally, the preparation method of the nano ZnMnO 3 oxide comprises the following steps: mixing a salt solution containing a Zn source and a Mn source with a precipitant at the water bath temperature of 60-80 ℃, mechanically stirring the mixed solution at the rotating speed of 300-1000r/min to be uniform, simultaneously adjusting the pH value to be 6-10 to cause coprecipitation reaction, filtering the obtained coprecipitation product, washing the product with deionized water, and finally roasting the product in a muffle furnace at the temperature of 300-700 ℃ to obtain the nano ZnMnO 3 oxide.
According to one aspect of the present application, there is provided a process for preparing aromatic hydrocarbons by contacting a feed gas comprising hydrogen and carbon monoxide with a catalyst, reacting II to obtain aromatic hydrocarbons; the catalyst is at least one selected from the catalysts described in any one of the above and the catalysts obtained according to the preparation method described in any one of the above.
Alternatively, the conditions of reaction II are: the reaction temperature is 250-450 ℃, the reaction pressure is 2-5 MPa, and the mass airspeed of the synthesis gas is 500-6000 h -1.
Optionally, the upper limit of the reaction temperature is selected from 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃; the lower limit is selected from 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃ or 440 ℃.
Alternatively, the upper limit of the reaction pressure is selected from 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 5MPa; the lower limit is selected from 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa or 4.5MPa.
Optionally, in the feed gas containing hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide is 1-3:1.
Optionally, the upper molar ratio of hydrogen to carbon monoxide is selected from 1.5:1, 2:1, 2.5:1 or 3:1; the lower limit is selected from 1:1, 1.5:1, 2:1 or 2.5:1.
Specifically, a catalyst is arranged in a reactor, and feed gas of H 2 and CO is introduced to contact and react with the catalyst to prepare the aromatic hydrocarbon.
The application has the beneficial effects that:
1) The preparation method of the catalyst provided by the invention has the advantages of simple preparation, mild conditions, easiness in repetition and capability of large-scale preparation. By changing the preparation conditions, the nano ZnMnO 3 oxide contained in the catalyst has adjustable particle size, specific surface area and pore volume, and can be applied to the reaction of directly converting synthesis gas into aromatic hydrocarbon.
2) Compared with the application of large-size metal oxide prepared by adopting the preparation method, the catalyst provided by the invention has the advantages that the catalytic activity is greatly improved, and the catalyst has more efficient reaction performance in the application of directly converting the synthesis gas into aromatic hydrocarbon.
Drawings
FIG. 1 is a scanning electron microscope image of a nano ZnMnO 3 oxide prepared according to the method in example 1 of the present application.
FIG. 2 is a scanning electron microscope image of a large-sized a-ZnMnO 3 oxide prepared according to the method in comparative example 1 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, with H-ZSM-5 being purchased from the university of south opening catalyst plant, unless otherwise specified.
The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.
The CO conversion and aromatics selectivity were both calculated on a carbon mole basis:
CO conversion = [ (moles of CO in feed) - (moles of CO in discharge) ] ≡ (moles of CO in feed) ×100%
Aromatic selectivity = (moles of aromatic carbon in the effluent)/(moles of carbon in all hydrocarbon products in the effluent) ×100%
Thermostatic water bath (instrument model: HH-M2; source: shanghai He Tian Kexue instruments Co., ltd.); mechanical stirrer (instrument model: ESJ-500; source: shanghai Yi Le mechanical equipment Co., ltd.); PH meter (instrument model: PHSJ-6L; source: shanghai Instrument electrosurgery instruments Co., ltd.); muffle furnace (instrument model: DC-B; source: beijing original science and technology Co., ltd.); gas chromatography (instrument model: 7890B; source: agilent technologies Co., ltd.); scanning electron microscopy (instrument model: hitachi-SU8080; source: hitachi high technology Co.); in a transmission electron microscope (instrument model: JEM-2100F; source: japanese electronics Co., ltd.); physical adsorption instrument (instrument model: ASAP 2020; source: america microphone instruments Co.).
Example 1 preparation of nano ZnMnO 3 oxide
Adopting a coprecipitation method to prepare nano-sized ZnMnO 3 oxide, wherein the condition of the coprecipitation method is as follows: the water bath temperature T is 70 ℃, the mechanical stirring rotating speed r is 500r/min, the pH value is 7.0, the roasting temperature T is 300 ℃, the metal salt is metal nitrate, the precipitant is ammonium carbonate, and the precipitant concentration is 1mol/L. The method comprises the following specific steps:
5.95g Zn source (NO 3)2·6H2 O and 7.16g 50wt% Mn (NO 3)2 aqueous solution are dissolved in 150mL deionized water to prepare corresponding mixed nitrate aqueous solution), the prepared nitrate aqueous solution and 1mol/L ammonium carbonate aqueous solution are added dropwise into a clean beaker together under the condition of heating in a water bath at 70 ℃ and continuous mechanical stirring rotation speed of 500r/min, the pH is controlled to be 7.0 until the mixed nitrate aqueous solution is completely added dropwise, the solution is kept stand for 3h and filtered by suction, and washed 5 times with 250mL deionized water, the obtained precipitate is dried in a baking oven at 120 ℃ for 12 h, the dried sample is placed in a muffle furnace, the temperature is raised to 300 ℃ at a heating rate of 2 ℃/min, and the roasting temperature is carried out at 300 ℃ for 4h, so as to prepare the nano ZnMnO 3 oxide.
Example 2 ZnMnO 3-T500、ZnMnO3 preparation of T700 oxide
The nano ZnMnO 3-T500、ZnMnO3 -T700 oxide was prepared by a method similar to that in example 1. Wherein, the difference from the method in example 1 is that the roasting temperature in the coprecipitation process is changed to 500 ℃ and 700 ℃ respectively, znMnO 3-T500、ZnMnO3 -T700 oxide is prepared respectively.
Example 3 preparation of ZnMnO 3-t60、ZnMnO3 -t80 oxide
The nano ZnMnO 3-t60、ZnMnO3 -t80 oxide was prepared by a method similar to that in example 1. Wherein, the difference from the method in example 1 is that the water bath temperature in the coprecipitation process is changed to 60℃and 80℃respectively, znMnO 3-t60、ZnMnO3 -t80 oxide is prepared respectively.
Example 4 ZnMnO 3-pH6、ZnMnO3 preparation of pH10 oxide
The preparation of nano ZnMnO 3-Ph6、ZnMnO3 -pH10 oxide was carried out in a similar way to that in example 1. Wherein, the difference from the method in example 1 is that the pH value in the coprecipitation process is respectively changed to 6.0 and 10.0, and ZnMnO 3-pH6、ZnMnO3 -pH10 oxide is respectively prepared.
Example 5 ZnMnO 3-r300、ZnMnO3 preparation of r1000 oxide
The nano ZnMnO 3-r300、ZnMnO3 -r1000 oxide was prepared by a method similar to that in example 1. Wherein, the difference from the method in example 1 is that the mechanical stirring rotation speed in the coprecipitation process is respectively changed to 300r/min and 1000r/min, and ZnMnO 3-r300、ZnMnO3 -r1000 oxide is respectively prepared.
EXAMPLE 6 ZnMnO 3-Y、ZnMnO3 preparation of L oxide
A method similar to that in example 1 was employed, except that nitrate was acetate and sulfate were replaced with Zn (CH 3COO)2·2H2 O) of the same number of moles as that of Zn (NO 3)2·6H2 O) in example 1, mn was replaced with Mn (CH 3COO)2) of the same number of moles as that of Mn (NO 3)2) in example 1, zn (NO 3)2·6H2 O) was replaced with ZnSO 4 of the same number of moles as that of Zn (NO 3)2·6H2 O) in example 1, mn was replaced with MnSO 4 of the same number of moles as that of Mn (NO 3)2) in example 1, and ZnMnO 3-S、ZnMnO3 -C oxide was produced, respectively.
EXAMPLE 7 ZnMnO 3 preparation of H oxide
A catalyst ZnMnO 3 -H oxide was prepared in a similar manner to that in example 1, except that ammonium carbonate was replaced by ammonium bicarbonate.
EXAMPLE 8 preparation of ZnMnO 3 -C oxide
A method similar to that in example 1 was employed, except that the concentration of the precipitant was changed to 3mol/L, the precipitate obtained by the reaction was dried in an oven at 120℃for 12 hours, the dried sample was placed in a muffle furnace, heated to 300℃at a heating rate of 3℃per minute, and calcined at a calcination temperature of 300℃for 5 hours to obtain ZnMnO 3 -C oxide.
Example 9 Zn 0.8MnO3、Zn1.2MnO3 preparation of oxide
The procedure was conducted in a similar manner to that in example 1, except that the amount of Zn source Zn (NO 3)2·6H2 O) added was changed, specifically, zn source Zn (NO 3)2·6H2 O was added in an amount of 4.76g and 7.14g, respectively, to obtain Zn 0.8MnO3、Zn1.2MnO3 oxide, respectively.
Comparative example 1
A large-size a-ZnMnO 3 oxide was produced by a method similar to that in example 1, except that the firing temperature was changed to 1000 ℃.
Comparative example 2
A large-size b-ZnMnO 3 oxide was prepared by a method similar to that in example 1, except that the water bath temperature was changed to 30℃close to room temperature.
Comparative example 3
A large-size c-ZnMnO 3 oxide was prepared by a method similar to that in example 1, except that the pH during the coprecipitation was changed to 5.0.
Comparative example 4
A large-size d-ZnMnO 3 oxide was prepared by a method similar to that in example 1, except that the mechanical stirring speed during coprecipitation was changed to 100 r/min.
Comparative example 5
A process similar to that of example 1 was used, except that the precipitant in the co-precipitation process was changed to urea, to produce a large size e-ZnMnO 3 oxide.
Comparative analysis of the prepared ZnMnO 3 oxide:
1) The nano ZnMnO 3 oxide prepared in examples 1 to 8 and the large-sized a-ZnMnO 3、b-ZnMnO3、c-ZnMnO3、d-ZnMnO3、e-ZnMnO3 oxide prepared in comparative examples 1 to 5 were respectively tested for particle size, specific surface area and pore volume.
The particle size testing method comprises the following steps: the oxide was dispersed in an ethanol solution and dropped onto a copper mesh, and then placed in a transmission electron microscope (instrument model: JEM-2100F), and the particle size was measured.
The specific surface area test method comprises the following steps: the oxide was placed in a physical adsorption instrument (instrument model: ASAP 2020) to test the specific surface area.
The pore volume testing method comprises the following steps: the oxide was placed in a physical adsorption instrument (instrument model: ASAP 2020) and the pore volume was measured.
The test results are shown in Table 1.
2) The nano ZnMnO 3 oxide prepared in example 1 according to the present application and the large-sized a-ZnMnO 3 oxide prepared by firing at 1000 ℃ in comparative example 1 according to the present application were each subjected to scanning electron microscope test (instrument model: hitachi-SU 8080). Among them, fig. 1 is a scanning electron microscope image of the nano ZnMnO 3 oxide prepared in example 1 according to the present application. FIG. 2 is a scanning electron microscope image of a large-sized a-ZnMnO 3 oxide prepared according to the method in comparative example 1 of the present application.
As can be seen by comparing fig. 1 and fig. 2: the particle size of the large-size a-ZnMnO 3 oxide which is not prepared by the method is larger, and the particle size of the nano ZnMnO 3 oxide which is prepared by the method is obviously reduced.
TABLE 1 structural parameters of nano ZnMnO 3 oxide prepared by the inventive method and of large size ZnMnO 3 oxide not prepared by the inventive method
By comparing the above data, it can be seen that: the a-ZnMnO 3、b-ZnMnO3、c-ZnMnO3、d-ZnMnO3、e-ZnMnO3 oxides prepared in comparative examples 1-5 all have larger sizes; the particle size of the serial nanometer ZnMnO 3 oxide prepared by the preparation method is obviously reduced, and the specific surface area and the pore volume are also greatly improved.
Example 10 use of the catalyst of the application in the preparation of aromatic hydrocarbons by direct conversion of synthesis gas
The nano ZnMnO 3 oxide prepared in example 1 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst 1# is obtained after granulation. The catalyst 1# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 350 ℃, the reaction pressure is 3MPa, the space velocity is 1500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
The nano ZnMnO 3 -T500 oxide prepared in the example 2 and H-ZSM-5 (SiO 2/Al2O3 =150) are ground and mixed uniformly according to the weight ratio of 1:1, and the catalyst 2# is obtained after granulation. The catalyst No. 2 is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 2:1, the reaction temperature is 450 ℃, the reaction pressure is 5MPa, the space velocity is 500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing the nano ZnMnO 3 -T700 prepared in the embodiment 2 and H-ZSM-5 (SiO 2/Al2O3 =160) uniformly according to the weight ratio of 5:1, and granulating to obtain the catalyst 3#. The catalyst 3# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 3:1, the reaction temperature is 250 ℃, the reaction pressure is 2MPa, the space velocity is 2000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing the nano ZnMnO 3 -t60 prepared in the embodiment 3 and H-ZSM-5 (SiO 2/Al2O3 =170) uniformly according to the weight ratio of 10:1, and granulating to obtain the catalyst No. 4. The catalyst 4# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 2:1, the reaction temperature is 400 ℃, the reaction pressure is 4MPa, the space velocity is 2500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing the nano ZnMnO 3 -t80 prepared in the embodiment 3 and H-ZSM-5 (SiO 2/Al2O3 =180) uniformly according to the weight ratio of 2:1, and granulating to obtain the catalyst No. 5. The catalyst No. 5 is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 3:1, the reaction temperature is 300 ℃, the reaction pressure is 3MPa, the space velocity is 3000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
The nano ZnMnO 3 -pH6 and H-ZSM-5 (SiO 2/Al2O3 =190) prepared in example 4 are ground and mixed uniformly according to the weight ratio of 6:1, and the catalyst 6# is obtained after granulation. The catalyst 6# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 2:1, the reaction temperature is 360 ℃, the reaction pressure is 4MPa, the space velocity is 4000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -pH10 and H-ZSM-5 (SiO 2/Al2O3 =200) prepared in example 4 uniformly according to a weight ratio of 8:1, and granulating to obtain the catalyst No. 7. The catalyst No. 7 is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 420 ℃, the reaction pressure is 2MPa, the space velocity is 5000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -r300 prepared in example 5 and H-ZSM-5 (SiO 2/Al2O3 =210) uniformly according to a weight ratio of 4:1, and granulating to obtain the catalyst 8#. The catalyst 8# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 320 ℃, the reaction pressure is 3MPa, the space velocity is 6000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing the nano ZnMnO 3 -r1000 prepared in the example 5 and H-ZSM-5 (SiO 2/Al2O3 =220) uniformly according to the weight ratio of 7:1, and granulating to obtain the catalyst 9#. The catalyst 9# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 3:1, the reaction temperature is 340 ℃, the reaction pressure is 3MPa, the space velocity is 4000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -Y prepared in example 6 and H-ZSM-5 (SiO 2/Al2O3 =230) uniformly according to a weight ratio of 4:1, and granulating to obtain the catalyst 10#. Catalyst 10# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 2:1, the reaction temperature is 360 ℃, the reaction pressure is 2.5MPa, the space velocity is 3000H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -L prepared in example 6 and H-ZSM-5 (SiO 2/Al2O3 =240) uniformly according to a weight ratio of 2:1, and granulating to obtain the catalyst 11#. Catalyst 11# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 330 ℃, the reaction pressure is 3.5MPa, the space velocity is 3500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -H and H-ZSM-5 (SiO 2/Al2O3 =250) prepared in example 7 uniformly according to a weight ratio of 7:1, and granulating to obtain the catalyst 12#. Catalyst 12# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 2:1, the reaction temperature is 370 ℃, the reaction pressure is 4.5MPa, the space velocity is 4500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Grinding and mixing nano ZnMnO 3 -C prepared in example 8 and H-ZSM-5 (SiO 2/Al2O3 =260) uniformly according to the weight ratio of 1:1, and granulating to obtain the catalyst No. 13. The catalyst 13# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 3:1, the reaction temperature is 380 ℃, the reaction pressure is 3MPa, the space velocity is 5500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
The nano Zn 0.8MnO3 oxide prepared in example 9 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst 14# is obtained after granulation. The catalyst No. 14 is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 350 ℃, the reaction pressure is 3MPa, the space velocity is 1500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
The nano Zn 1.2MnO3 oxide prepared in example 9 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst 15# is obtained after granulation. The catalyst 15# is placed in a reactor, H 2 and CO synthesis gas are introduced, the molar ratio of H 2 to CO is 1:1, the reaction temperature is 350 ℃, the reaction pressure is 3MPa, the space velocity is 1500H -1, the reaction for preparing aromatic hydrocarbon from the synthesis gas is carried out, and the reaction results are shown in Table 2.
Comparative example 6 application of catalyst prepared from large-sized a-ZnMnO 3、b-ZnMnO3、c-ZnMnO3、d-ZnMnO3、e-ZnMnO3 oxide and H-ZSM-5 in preparation of aromatic hydrocarbon by direct conversion of synthesis gas
The large-size a-ZnMnO 3 oxide prepared in comparative example 1 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst comparative example 1# is obtained after granulation. Catalyst comparative example 1# was placed in a reactor, H 2 and CO synthesis gas were introduced, the molar ratio of H 2 and CO was 1:1, the reaction temperature was 350 ℃, the reaction pressure was 3MPa, the space velocity was 1500H -1, the synthesis gas to aromatics reaction was carried out, and the reaction results are shown in Table 2.
The large-size b-ZnMnO 3 oxide prepared in comparative example 2 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst comparative example 2# is obtained after granulation. Catalyst comparative example 2# was placed in a reactor, H 2 and CO synthesis gas were introduced, the molar ratio of H 2 and CO was 1:1, the reaction temperature was 350 ℃, the reaction pressure was 3MPa, the space velocity was 1500H -1, the synthesis gas to aromatics reaction was carried out, and the reaction results are shown in Table 2.
The large-sized c-ZnMnO 3 oxide prepared in comparative example 3 and H-ZSM-5 (SiO 2/Al2O3 =140) were ground and mixed uniformly in a weight ratio of 3:1, and the catalyst comparative example 3# was obtained after granulation. Catalyst comparative example 3# was placed in a reactor, H 2 and CO synthesis gas were introduced, the molar ratio of H 2 and CO was 1:1, the reaction temperature was 350 ℃, the reaction pressure was 3MPa, the space velocity was 1500H -1, the synthesis gas to aromatics reaction was carried out, and the reaction results are shown in Table 2.
The large-size d-ZnMnO 3 oxide prepared in comparative example 4 and H-ZSM-5 (SiO 2/Al2O3 =140) were ground and mixed uniformly in a weight ratio of 3:1, and the catalyst comparative example 4# was obtained after granulation. Catalyst comparative example 4# was placed in a reactor, H 2 and CO synthesis gas were introduced, the molar ratio of H 2 and CO was 1:1, the reaction temperature was 350 ℃, the reaction pressure was 3MPa, the space velocity was 1500H -1, the synthesis gas to aromatics reaction was carried out, and the reaction results are shown in Table 2.
The large-size e-ZnMnO 3 oxide prepared in comparative example 5 and H-ZSM-5 (SiO 2/Al2O3 =140) are ground and mixed uniformly according to the weight ratio of 3:1, and the catalyst comparative example 5# is obtained after granulation. Catalyst comparative example 5# was placed in a reactor, H 2 and CO synthesis gas were introduced, the molar ratio of H 2 and CO was 1:1, the reaction temperature was 350 ℃, the reaction pressure was 3MPa, the space velocity was 1500H -1, the synthesis gas to aromatics reaction was carried out, and the reaction results are shown in Table 2.
TABLE 2 reaction results of catalysts in the direct conversion of Synthesis gas to aromatics
From the above analysis of the data, it can be seen that: the catalyst containing the nano ZnMnO 3 oxide prepared by the preparation method can greatly improve the CO conversion rate and the aromatic selectivity of the reaction of preparing aromatic hydrocarbon (including benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene and the like) by converting the synthesis gas, and the CO conversion rate and the aromatic selectivity can be respectively maintained to be more than 50% and 74%, and respectively can be up to 80% and 85%. And the CO conversion rate and the aromatic hydrocarbon selectivity of the catalyst containing the large-size a-ZnMnO 3、b-ZnMnO3、c-ZnMnO3、d-ZnMnO3、e-ZnMnO3 oxide which is not prepared by the preparation method are relatively low. Therefore, the catalyst containing the nano ZnMnO 3 oxide prepared by the preparation method provided by the invention can greatly improve the catalytic activity in the application of directly converting the synthesis gas into aromatic hydrocarbon, and simultaneously has high conversion rate, high aromatic hydrocarbon selectivity and higher efficient reaction performance.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (13)

1. A catalyst for preparing aromatic hydrocarbon from synthesis gas, which is characterized by comprising nano ZnMnO 3 oxide and a silicon-aluminum molecular sieve;
the particle size of the nano ZnMnO 3 oxide is 3-30 nm;
the specific surface area of the nano ZnMnO 3 oxide is 50-1000 m 2/g;
The pore volume of the nano ZnMnO 3 oxide is 10-300 cm 3/g;
the mass ratio of the nano ZnMnO 3 oxide to the silicon-aluminum molecular sieve is 1-10:1;
the silicon-aluminum molecular sieve is selected from ZSM-5 molecular sieves;
The preparation method of the catalyst comprises the following steps:
(1) Obtaining nano ZnMnO 3 oxide;
(2) Mixing the nano ZnMnO 3 oxide with a silicon-aluminum molecular sieve to obtain the catalyst;
the preparation method of the nano ZnMnO 3 oxide comprises the following steps:
(i) Mixing materials containing Zn sources, mn sources and precipitants, regulating the pH value to 6-10, and reacting I to obtain an intermediate product I;
(ii) Roasting the intermediate product I to obtain the nano ZnMnO 3 oxide.
2. The catalyst for the production of aromatic hydrocarbons from synthesis gas according to claim 1, wherein the silica-alumina molecular sieve has a silica-alumina ratio of: siO 2/Al2O3 =140 to 260.
3. The catalyst for the production of aromatic hydrocarbons from synthesis gas according to claim 1, wherein the Zn source is selected from at least one of the soluble salts of zinc;
the Mn source is selected from at least one of soluble salts of manganese.
4. The catalyst for producing aromatic hydrocarbon from synthetic gas according to claim 1, wherein the Zn source is at least one selected from the group consisting of nitrate, acetate, chloride and sulfate of zinc;
the Mn source is selected from at least one of nitrate, acetate, chloride and sulfate of manganese.
5. The catalyst for preparing aromatic hydrocarbon from synthetic gas according to claim 1, wherein the molar ratio of Zn in the Zn source to Mn in the Mn source is 0.8-1.2: 1.
6. The catalyst for preparing aromatic hydrocarbon from synthetic gas according to claim 1, wherein the temperature of the reaction I is 60-80 ℃.
7. The catalyst for the production of aromatic hydrocarbons from synthesis gas according to claim 1, wherein in step (i), stirring is further included; the stirring is mechanical stirring; the rotating speed of the mechanical stirring is 300-1000 r/min.
8. The catalyst for the production of aromatic hydrocarbons from synthesis gas according to claim 1, wherein the calcination conditions are: the temperature is 300-700 ℃ and the time is 3-5 h.
9. The catalyst for the production of aromatic hydrocarbons from synthesis gas according to claim 1, wherein the mass containing Zn source, mn source and precipitant further comprises a solvent; the solvent is at least one selected from water, ethanol and N, N-dimethylformamide.
10. The catalyst for preparing aromatic hydrocarbon from synthetic gas according to claim 1, wherein the precipitant is at least one selected from ammonium carbonate and ammonium bicarbonate.
11. A method for preparing aromatic hydrocarbon is characterized in that raw material gas containing hydrogen and carbon monoxide is contacted with a catalyst, and reaction II is carried out to obtain aromatic hydrocarbon;
the catalyst is selected from the catalysts of any one of claims 1 to 10.
12. The method according to claim 11, wherein the conditions of reaction II are: the reaction temperature is 250-450 ℃, the reaction pressure is 2-5 MPa, and the mass airspeed of the synthesis gas is 500-6000 h -1.
13. The method of claim 11, wherein the molar ratio of hydrogen to carbon monoxide in the feed gas comprising hydrogen and carbon monoxide is 1-3:1.
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