CN110496639B - Catalyst for aromatic hydrocarbon synthesis and preparation method and application thereof - Google Patents
Catalyst for aromatic hydrocarbon synthesis and preparation method and application thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- 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
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- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Abstract
The invention discloses a catalyst for aromatic hydrocarbon synthesis and a preparation method and application thereof. The catalyst comprises zinc-aluminum spinel oxide and an acidic molecular sieve in a mass ratio of 1: 5-5: 1, wherein the zinc-aluminum spinel oxide optionally contains at least one other element selected from chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from acidic ZSM-5 molecular sieve, acidic ZSM-11 molecular sieve and a mixture thereof. When the catalyst is applied to a method for directly preparing aromatic hydrocarbon by carbon dioxide hydrogenation, the carbon dioxide hydrogenation can be carried out to generate the aromatic hydrocarbon with high selectivity, and the catalyst has good stability. The method provided by the invention realizes the one-step generation of the aromatic hydrocarbon by carbon dioxide hydrogenation, and reduces the problem of large energy consumption caused by step-by-step production.
Description
Technical Field
The invention relates to a catalyst for aromatic hydrocarbon synthesis and a preparation method and application thereof.
Background
Since nearly two centuries, petrochemical resources represented by petroleum, coal and natural gas are developed and utilized on a large scale, abundant energy and raw materials are provided for the human society, and the unprecedented and prosperous development of economy and civilization is promoted. However, this also leads to a large carbon dioxide emission. Carbon dioxide is known to be a typical greenhouse effect gas, and large-scale industrial emission poses serious threats to human living environment. Clean energy represented by solar energy, wind energy, tidal energy, geothermal energy and the like has large total energy, does not generate extra carbon dioxide emission, and is difficult to efficiently utilize due to the defects of low energy density, large fluctuation and the like. If water is electrolyzed by using electric energy generated by clean energy to obtain hydrogen, and then the hydrogen reacts with carbon dioxide generated by petrochemical resources to prepare bulk fuels or chemicals, the two problems can be effectively solved.
Aromatic hydrocarbon is an important basic organic chemical raw material, and derivatives thereof are widely used in chemical products such as fuels, petrifaction products, chemical fibers, plastics, rubber and the like and fine chemicals. At present, aromatic hydrocarbon is mainly produced by using petroleum as a raw material and mainly comes from a catalytic reforming process unit of an oil refinery. In addition, the aromatic hydrocarbon production process in the petroleum route also comprises an aromatic hydrocarbon extraction technology, a heavy aromatic hydrocarbon lightening technology and a light hydrocarbon aromatization technology. For countries with energy structures rich in coal and lean in oil, such as China, aromatics can also be produced through coal chemical engineering routes. In the technology for preparing aromatic hydrocarbon in coal chemical industry, the technical research for preparing aromatic hydrocarbon by taking methanol which is a platform product in coal chemical industry as a raw material is the most extensive. The technology for preparing aromatic hydrocarbon from methanol generally adopts metal modified acidic ZSM-5 molecular sieve catalyst such as zinc, gallium, silver and the like, but the factors of fast aromatic hydrocarbon selectivity reduction, short catalyst service life and the like restrict the large-scale industrial application of the technology for preparing aromatic hydrocarbon from methanol.
Because the aromatic hydrocarbon has large unsaturation degree and complex molecular structure, the preparation is difficult in a strong reduction reaction environment. At present, no research report on the direct high-selectivity preparation of aromatic hydrocarbon by carbon dioxide hydrogenation is found.
Disclosure of Invention
The present inventors have made diligent studies in order to overcome the problems occurring in the prior art. As a result, they have found that a catalyst comprising a zinc aluminum spinel oxide and an acidic molecular sieve is very suitable for a process for producing aromatic hydrocarbons by hydrogenation of carbon dioxide, and have accomplished the present invention.
Accordingly, it is an object of the present invention to provide a catalyst for synthesis of aromatic hydrocarbons, which comprises zinc aluminate spinel oxide and acidic molecular sieve in a mass ratio of 1: 5 to 5: 1, wherein the zinc aluminate spinel oxide optionally contains at least one other element selected from chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from acidic ZSM-5 molecular sieve, acidic ZSM-11 molecular sieve and a mixture thereof.
It is another object of the present invention to provide a process for preparing the above catalyst.
It is still another object of the present invention to provide a process for producing aromatic hydrocarbons by hydrogenation of carbon dioxide using the above catalyst.
Description of the preferred embodiments
In a first aspect, the present invention provides a catalyst for aromatic hydrocarbon synthesis, which comprises zinc aluminate spinel oxide and an acidic molecular sieve in a mass ratio of 1: 5 to 5: 1, wherein the zinc aluminate spinel oxide optionally contains at least one other element selected from chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from acidic ZSM-5 molecular sieve, acidic ZSM-11 molecular sieve and a mixture thereof.
In the catalyst, the mass ratio of the zinc aluminate spinel oxide to the acidic molecular sieve is 1: 5-5: 1, such as 1: 1, 1: 5, 2: 1 or 5: 1.
The molar ratio of Zn to Al in the zinc aluminate spinel oxide of the present invention is any ratio, preferably 1: 9 to 1: 1, such as 1: 1, 1: 2, 1: 4.5 or 1: 9.
In some embodiments, the zinc aluminate spinel oxide has a zinc aluminate spinel crystal size of less than or equal to 30 nm.
In some embodiments, the zinc aluminum spinel oxide further comprises at least one other element selected from the group consisting of chromium, zirconium, copper, manganese, indium, gallium, and silicon. The other elements may be added to the zinc aluminum spinel oxide by one or both of impregnation or coprecipitation. Preferably, the mass fraction of said other elements in the zinc aluminate spinel oxide is less than or equal to 10%, such as 1%, 3%, 5%, 7%, 9% or 10%.
The acidic molecular sieve in the catalyst of the present invention is selected from the group consisting of acidic ZSM-5 molecular sieves, acidic ZSM-11 molecular sieves, and mixtures thereof.
In some embodiments, the acidic ZSM-5 and ZSM-11 molecular sieves have an atomic ratio of silicon to aluminum of 3 to 200, preferably 100 to 150.
In some embodiments, the crystals of the acidic ZSM-5 and ZSM-11 molecular sieves are of micron or nanometer scale, and the crystals contain a microporous or meso-microporous structure.
The acidic molecular sieves useful in the present invention are commercially available or can be prepared by methods known per se.
The catalyst of the present invention may have any shape and size known in the art to be suitable for use in fixed bed reactor applications. For example, the catalyst may be in the shape of spheres, cylinders, semicylindrical, prisms, clover, rings, pellets, regular or irregular particles, or tablets. In a second aspect, the present invention provides a process for preparing the above catalyst, the process comprising the steps of:
(1) providing a zinc aluminum spinel oxide, wherein the zinc aluminum spinel oxide optionally contains at least one other element selected from the group consisting of chromium, zirconium, copper, manganese, indium, gallium, and silicon;
(2) providing an acidic molecular sieve selected from the group consisting of acidic ZSM-5 molecular sieves, acidic ZSM-11 molecular sieves, and mixtures thereof;
(3) mixing the zinc aluminum spinel oxide obtained in the step (1) and the acidic molecular sieve obtained in the step (2), and molding the obtained mixture.
In one embodiment, the zinc aluminate spinel oxide useful in preparing the catalyst of the invention is prepared by a precipitation-calcination process, optionally with the addition of at least one other element. For example, the zinc aluminate spinel oxide is prepared by a process comprising the steps of: preparing a zinc salt and an aluminum salt into a mixed metal salt aqueous solution; contacting the aqueous mixed metal salt solution with an aqueous precipitant solution to co-precipitate metal ions in the aqueous mixed metal salt solution; aging; washing, drying and calcining the precipitate to obtain the zinc-aluminum spinel oxide; and optionally adding at least one other element by impregnation and/or co-precipitation of a brine solution of the at least one other element. Examples of such precipitants include, but are not limited to, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide, and mixtures thereof.
In one embodiment, the temperature during the co-precipitation is 20 ℃ to 95 ℃, the pH during the co-precipitation is 7.0 to 9.0, the aging time is not less than 1 hour, and the calcination temperature is 450 ℃ to 800 ℃.
In one embodiment, the zinc aluminate spinel oxide is prepared as follows: dissolving zinc salt and aluminum salt in any proportion in deionized water to prepare a mixed metal salt water solution, wherein the concentration of the mixed metal salt water solution is any concentration which can be completely dissolved in the deionized water at room temperature; dissolving a precipitator in deionized water to prepare a precipitator aqueous solution, wherein the concentration of the precipitator aqueous solution is any concentration which can be completely dissolved in the deionized water at room temperature; and (2) contacting the mixed metal salt aqueous solution with the precipitant aqueous solution, and carrying out coprecipitation at 20-95 ℃, wherein the pH value is controlled to be 7.0-9.0 by controlling the flow rates of the mixed metal salt aqueous solution and the precipitant aqueous solution in the precipitation process. And after the coprecipitation is finished, aging for 1-24 h at 20-95 ℃, then performing centrifugal separation, washing with deionized water, drying for 24h at 100 ℃, and finally calcining for 2-10 h at 450-800 ℃ to obtain the zinc-aluminum spinel oxide.
In the present invention, there is no particular limitation on the kinds of the zinc salt, the aluminum salt and the salt of at least one other element as long as they are water-soluble, for example, have a water solubility of more than 1g/L at 25 ℃. Examples of the salts of the zinc salt, the aluminum salt, and the at least one other element include, but are not limited to, hydrochloride, sulfate, and nitrate.
In the method of the present invention, the manner of contacting the aqueous solution of the mixed metal salt with the aqueous solution of the precipitant is not particularly limited. In a particular embodiment, the contacting may be accomplished in a co-current feed, a forward feed, or a reverse feed.
The acidic molecular sieve that may be used in the catalyst preparation process of the present invention is selected from the group consisting of acidic ZSM-5 molecular sieves, acidic ZSM-11 molecular sieves, and mixtures thereof. The acidic molecular sieves are commercially available or can be prepared by methods known per se.
There is no particular limitation on the molding method employed in step (3) of the catalyst preparation method of the present invention. For example, the mixture can be molded into a catalyst shape suitable for fixed bed reactor applications using an extrusion process or a molding process.
In a third aspect, the present invention provides a method for preparing aromatic hydrocarbons by hydrogenating carbon dioxide, comprising:
a) passing a feed gas comprising carbon dioxide and hydrogen through a catalyst-loaded reaction zone under reaction conditions sufficient to convert at least a portion of the feed to yield a reaction effluent comprising aromatic hydrocarbons; and
b) separating the aromatic hydrocarbon from the reaction effluent.
It is believed that the reactions occurring in the reaction zone are very complex and involve a series of reaction processes, such as:
1) methanol synthesis reaction:
CO2+3H2＝CH3OH+H2O
2) reaction for preparing aromatic hydrocarbon from methanol:
CH3OH → arene + H2O
3) Reverse water gas shift Reaction (RWGS):
CO2+H2＝CO+H2O
the catalyst in the method comprises zinc-aluminum spinel oxide and an acidic molecular sieve in a mass ratio of 1: 5-5: 1, wherein the zinc-aluminum spinel oxide optionally contains at least one other element selected from chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from acidic ZSM-5 molecular sieve, acidic ZSM-11 molecular sieve and a mixture thereof. The details of the catalyst are as described in the first aspect of the invention.
In the process of the present invention, carbon dioxide and hydrogen are used as feed gases. In the raw material gas, the molar ratio of hydrogen to carbon dioxide is 1: 9-9: 1, preferably 1: 9-1: 1.
The main side reaction in the reaction for preparing the aromatic hydrocarbon by the carbon dioxide hydrogenation is a reverse water gas shift reaction which is a typical equilibrium reaction, and the addition of the carbon monoxide is beneficial to inhibiting the reverse water gas shift reaction and improving the utilization efficiency of the carbon dioxide. Therefore, the feed gas in the method of the present invention may further contain carbon monoxide, and the molar concentration of carbon monoxide in the feed gas is 1.0 to 20.0%, for example, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 17%, and 20%.
In the process of the present invention, the reaction zone may be one or more fixed bed reactors. The fixed bed reactor may be operated in a continuous mode. When multiple fixed bed reactors are employed, the multiple reactors may be in series, parallel, or a combination of series and parallel configurations.
In the method of the present invention, the reaction conditions include: the reaction temperature of 300-450 ℃, the reaction pressure of 0.5-10.0 MPa, the molar ratio of hydrogen to carbon dioxide in the feed gas of 1: 9-9: 1, and the reaction time of 1000-20000 h-1The synthesis gas volume is small hourly space velocity under the standard state of (1).
In a preferred embodiment, the reaction conditions include: reaction temperature of 310-360 ℃, reaction pressure of 1.0-4.0 MPa, molar ratio of hydrogen to carbon dioxide in feed gas of 3: 1-6: 1, and reaction time of 3000-8000 h-1The synthesis gas volume is small hourly space velocity under the standard state of (1).
In the invention, the arene is at least one selected from monocyclic arene containing 6-11 carbon atoms. Examples of the monocyclic aromatic hydrocarbon having 6 to 11 carbon atoms include, but are not limited to, benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, mesitylene, and durene.
The invention can produce the beneficial effects that:
1) the catalyst used in the invention can hydrogenate carbon dioxide to generate aromatic hydrocarbon with high selectivity, and has good stability.
2) By adding carbon monoxide, the reverse water gas shift reaction can be effectively inhibited, and the utilization efficiency of carbon dioxide is high.
3) The method provided by the invention realizes the one-step generation of the aromatic hydrocarbon by carbon dioxide hydrogenation, and reduces the problem of large energy consumption caused by step-by-step production.
Drawings
Fig. 1 is an XRD pattern of material a in example 1 of the present application.
FIG. 2 is a TEM image of material A in example 1 of the present application.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present invention were purchased commercially.
In an embodiment, two Agilent7890 gas chromatographs with gas autosampler, TCD detector connected to TDX-1 packed column, and FID detector connected to FFAP and PLOT-Q capillary columns were used for automated analysis.
In the examples, conversion and selectivity are calculated on a carbon mole basis:
carbon dioxide conversion rate ═ carbon dioxide carbon moles in feed) - (carbon dioxide carbon moles in discharge) ]/(carbon dioxide carbon moles in feed) × 100%
Arene selectivity (arene carbon mole number in discharged material) ÷ (carbon mole number sum of all hydrocarbon products, methanol and dimethyl ether in discharged material) × 100%
Carbon monoxide selectivity (moles of carbon monoxide produced by the reaction) ÷ (moles of carbon dioxide converted) × 100%
Preparation of zinc aluminum spinel oxide
Example 1
95g of Zn (NO)3)26H2O and 80g Al (NO)3)39H2O is dissolved in 200ml of deionized water to prepare a salt solution. 25g of ammonium carbonate was dissolved in 200ml of deionized water to prepare an alkali solution. And (3) respectively carrying out parallel flow mixing and coprecipitation on the salt solution and the alkali solution by using two peristaltic pumps, controlling the precipitation reaction temperature at 60 ℃, controlling the pH value at 7.2, aging for 4 hours at the temperature, filtering, washing, drying for 24 hours at 100 ℃, and calcining for 4 hours at 500 ℃ to obtain the zinc-aluminum spinel oxide with the number of A. X-ray fluorescence spectroscopy (XRF) showed Zn/Al (molar ratio) 1: 1 in a, with an XRD pattern as shown in fig. 1 and a TEM pattern as shown in fig. 2.
Example 2
48g of Zn (NO)3)26H2O and 80g Al (NO)3)39H2O is dissolved in 200ml of deionized water to prepare a salt solution. 25g of ammonia (containing 25% NH)3) Dissolving in 200ml deionized water to prepare alkali solution. And (3) respectively carrying out parallel flow mixing and coprecipitation on the salt solution and the alkali solution by using two peristaltic pumps, controlling the precipitation reaction temperature at 70 ℃, controlling the pH value at 7.5, aging for 6 hours at the temperature, filtering, washing, drying for 24 hours at 100 ℃, and calcining for 4 hours at 500 ℃ to obtain the zinc-aluminum spinel oxide with the number of B. XRF showed Zn/Al (molar ratio) of 1: 2 in B.
Example 3
10.6g of Zn (NO)3)26H2O and 80gAl (NO)3)39H2O is dissolved in 200ml of deionized water to prepare a salt solution. 25g of sodium carbonate is dissolved in 200ml of deionized water to prepare an alkali solution. And (3) respectively carrying out parallel flow mixing and coprecipitation on the salt solution and the alkali solution by using two peristaltic pumps, controlling the precipitation reaction temperature at 80 ℃, controlling the pH value at 7.8, aging for 6h at the temperature, filtering, washing, drying for 24h at 100 ℃, and calcining for 6h at 500 ℃ to obtain the zinc-aluminum spinel oxide with the number of C. XRF showed Zn/Al (molar ratio) of 1: 9 in C.
Example 4
10.6g of Zn (NO)3)26H2O with 40g Al (NO)3)39H2O is dissolved in 200ml of deionized water to prepare a salt solution. 15g of potassium carbonate was dissolved in 200ml of deionized water to prepare an alkali solution. And (3) respectively carrying out parallel flow mixing and coprecipitation on the salt solution and the alkali solution by using two peristaltic pumps, controlling the precipitation reaction temperature at 70 ℃, controlling the pH value at 7.1, aging for 6 hours at the temperature, filtering, washing, drying for 24 hours at 100 ℃, and calcining for 4 hours at 500 ℃ to obtain the zinc-aluminum spinel oxide with the number of D. XRF showed Zn/Al (molar ratio) of 1: 4.5 in D.
Example 5
Taking 7.7g of Cr (NO)3)39H2Dissolving O in 15ml of deionized water, then soaking 20g of catalyst B at room temperature for 24h, drying at 100 ℃ for 24h, and calcining at 500 ℃ for 4h to obtain 5% (mass fraction) of chromium-modified zinc-aluminum spinel oxide, wherein the number of the chromium-modified zinc-aluminum spinel oxide is E.
Example 6
Take 4.7g Zr(NO3)45H2Dissolving O in 15ml of deionized water, then impregnating 20g of catalyst B at room temperature for 24h, drying at 100 ℃ for 24h, and calcining at 500 ℃ for 4h to obtain 5% (mass fraction) of zirconium-modified zinc-aluminum spinel oxide, wherein the number of the zirconium-modified zinc-aluminum spinel oxide is F.
Catalyst preparation
Example 7
The zinc aluminate spinel oxide A and H-ZSM-5(Si/Al ═ 200) (catalyst factory of southern Kaiki university) were uniformly mixed at a mass ratio of 1: 1, ground with an agate mortar for 10 minutes, and then tabletted with a tabletting machine at 40MPa to prepare a physical mixed catalyst G.
Example 8
The zinc aluminum spinel oxide B and (Si/Al ═ 150) (catalyst factory, southern kaiko university) were mixed uniformly at a mass ratio of 2: 1, ground with an agate mortar for 10 minutes, and then tabletted with a tablet press at 40MPa to prepare a physically mixed catalyst H.
Example 9
The zinc aluminate spinel oxide C and H-ZSM-11 (Si/Al-40) (Oakco) were mixed uniformly at a mass ratio of 5: 1, ground for 10 minutes in an agate mortar, and then tabletted at 40MPa with a tabletting machine to prepare a physical mixed catalyst I.
Example 10
The zinc aluminate spinel oxide D and H-ZSM-5(Si/Al ═ 3) (Oakco) were mixed uniformly in a mass ratio of 1: 5, ground for 10 minutes with an agate mortar, and then tabletted with a tabletting machine at 40MPa to prepare a physical mixed catalyst J.
Example 11
The zinc aluminate spinel oxide E and H-ZSM-5(Si/Al 150) (catalyst works of southern Kai university) are uniformly mixed in a mass ratio of 2: 1, ground for 10 minutes by an agate grinding bowl, and then tabletted by a tabletting machine under 40MPa to prepare the physical mixed catalyst K.
Example 12
The zinc aluminate spinel oxide G and H-ZSM-5(Si/Al 150) (catalyst works of southern Kai university) are uniformly mixed in a mass ratio of 2: 1, ground for 10 minutes by an agate mortar, and then tabletted by a tabletting machine under 40MPa to prepare the physical mixed catalyst L.
Testing of catalyst Performance
Example 13
Crushing and screening the catalyst G into particles of 0.4-0.8 mm, putting 2G of the catalyst G into a stainless steel reaction tube with the inner diameter of 8mm, activating the catalyst G for 1h at 300 ℃ by using 50ml/min of hydrogen, and reacting under the following conditions: the reaction temperature (T) is 320 ℃, the reaction pressure (P) is 4.0MPa, and the molar ratio of hydrogen to carbon dioxide in the raw material gas is (H)2∶CO2) 3: 1; under standard condition, volume hourly space velocity (GHSV) of raw material gas is 6000h-1. After 500h of reaction, the product was analyzed by gas chromatography and the results are shown in Table 1.
Examples 14 to 18
The reaction conditions and the reaction results are shown in Table 1. The other operations were the same as in example 13.
Example 19
Crushing and screening the catalyst G into particles of 0.4-0.8 mm, loading 2G of the catalyst G into a stainless steel reaction tube with the inner diameter of 8mm, activating the catalyst G for 1h at 300 ℃ by using 50ml/min of hydrogen, and reacting under the following conditions: the reaction temperature (T) is 320 ℃, the reaction pressure (P) is 4.0MPa, and the molar ratio of hydrogen, carbon dioxide and carbon monoxide in the raw material gas is (H)2∶CO2CO is 3: 1: 0.04 (namely the content of CO in the raw material gas is 1 percent); under standard condition, volume hourly space velocity (GHSV) of raw material gas is 6000h-1. After 500h of reaction, the product was analyzed by gas chromatography and the results are shown in Table 1.
Example 20
Crushing and screening the catalyst G into particles of 0.4-0.8 mm, loading 2G of the catalyst G into a stainless steel reaction tube with the inner diameter of 8mm, activating the catalyst G for 1h at 300 ℃ by using 50ml/min of hydrogen, and reacting under the following conditions: the reaction temperature (T) is 320 ℃, the reaction pressure (P) is 4.0MPa, and the molar ratio of hydrogen, carbon dioxide and carbon monoxide in the raw material gas is (H)2∶CO2CO is 3: 1: 0.2 (namely the content of CO in the raw material gas is 4.8%); under standard condition, volume hourly space velocity (GHSV) of raw material gas is 6000h-1. After 500h of reaction, the product was analyzed by gas chromatography and the results are shown in Table 1.
Example 21
Crushing and screening the catalyst G into particles of 0.4-0.8 mm,2g of the mixture is put into a stainless steel reaction tube with the inner diameter of 8mm, and activated for 1h at 300 ℃ by 50ml/min of hydrogen to react under the following conditions: the reaction temperature (T) is 320 ℃, the reaction pressure (P) is 4.0MPa, and the molar ratio of hydrogen, carbon dioxide and carbon monoxide in the raw material gas is (H)2∶CO2CO is 3: 1 (namely the content of CO in the raw material gas is 20 percent); under standard condition, volume hourly space velocity (GHSV) of raw material gas is 6000h-1. After 500h of reaction, the product was analyzed by gas chromatography and the results are shown in Table 1.
TABLE 1 results of catalytic reactions in examples 13-21
Catalyst regeneration Performance test
Example 22
The deactivated catalyst in example 13 was treated at 550 ℃ for 10 hours with a mixed gas of 2% by volume of oxygen and 98% by volume of nitrogen, so that the catalyst was regenerated and reacted under the conditions of example 13. Five rounds of reaction were repeated in the same manner, and the catalytic activity data after 500 hours of reaction in each round were selected for comparison, and the results are shown in table 2.
TABLE 2 catalytic reaction results in example 22
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A method for preparing aromatic hydrocarbon by hydrogenating carbon dioxide comprises the following steps:
a) passing a feed gas comprising carbon dioxide and hydrogen through a catalyst-loaded reaction zone under reaction conditions sufficient to convert at least a portion of the feed to yield a reaction effluent comprising aromatic hydrocarbons; and
b) separating the aromatic hydrocarbon from the reaction effluent,
wherein the catalyst comprises zinc aluminate spinel oxide and an acidic molecular sieve in a mass ratio of 1: 5-5: 1, wherein the zinc aluminate spinel oxide optionally contains at least one other element selected from chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from acidic ZSM-5 molecular sieve, acidic ZSM-11 molecular sieve and a mixture thereof, and the atomic ratio of silicon to aluminum in the acidic ZSM-5 and ZSM-11 molecular sieves is 100-150; the Zn/Al molar ratio in the zinc-aluminum spinel oxide is 1: 9-1: 1; and the mass fraction of the other elements in the zinc aluminum spinel oxide is less than or equal to 10%;
wherein, the method for preparing the catalyst comprises the following steps:
(1) providing a zinc aluminum spinel oxide, wherein the zinc aluminum spinel oxide optionally contains at least one other element selected from the group consisting of chromium, zirconium, copper, manganese, indium, gallium, and silicon;
(2) providing an acidic molecular sieve selected from the group consisting of acidic ZSM-5 molecular sieves, acidic ZSM-11 molecular sieves, and mixtures thereof;
(3) and (3) uniformly mixing the zinc-aluminum spinel oxide obtained in the step (1) and the acidic molecular sieve obtained in the step (2), grinding the mixture by using an agate mortar, and tabletting the mixture by using a tabletting machine.
2. The method of claim 1, having at least one of the following features:
-the reaction zone comprises one fixed bed reactor, or a plurality of fixed bed reactors connected in series and/or in parallel;
-the reaction conditions comprise: reaction temperature of 300-450 ℃, reaction pressure of 0.5-10.0 MPa, and reaction pressure of 1: 9-9: 1 of hydrogen and carbon dioxide in feed gasThe molar ratio, and 1000-20000 h-1The synthesis gas volume is small hourly space velocity in the standard state;
-the aromatic hydrocarbon is at least one selected from monocyclic aromatic hydrocarbons having 6 to 11 carbon atoms.
3. The method of claim 1 or 2, wherein the feed gas further comprises carbon monoxide, and the molar concentration of the carbon monoxide in the feed gas is 1.0-20.0%.
4. The method of claim 2, wherein the reaction conditions are: reaction temperature of 310-360 ℃, reaction pressure of 1.0-4.0 MPa, molar ratio of hydrogen to carbon dioxide in feed gas of 3: 1-6: 1, and reaction time of 3000-8000 h-1The synthesis gas volume is small hourly space velocity under the standard state of (1).
5. The process of claim 1, wherein in step (1), the zinc aluminum spinel oxide is prepared by a precipitation-calcination process, and optionally at least one additional element is added.
6. The process of claim 5, wherein in step (1), the zinc aluminate spinel oxide is prepared by a process comprising: preparing a zinc salt and an aluminum salt into a mixed metal salt aqueous solution; contacting the aqueous mixed metal salt solution with an aqueous precipitant solution to co-precipitate metal ions in the aqueous mixed metal salt solution; aging; washing, drying and calcining the precipitate to obtain the zinc-aluminum spinel oxide; and optionally adding at least one other element by impregnation and/or co-precipitation of a brine solution of the at least one other element.
7. The method of claim 6, having at least one of the following characteristics:
-the salts of zinc, aluminium and at least one other element are selected from the group consisting of hydrochloride, sulphate and nitrate;
-the precipitating agent is selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and mixtures thereof;
-the co-precipitation is carried out at 20 ℃ to 95 ℃;
-the pH during the co-precipitation is 7.0 to 9.0;
-said ageing time is not less than 1 hour;
-the calcination is carried out at 450 to 800 ℃.
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