CN115180593B - Method for preparing high-added-value product by reforming light-driven carbonate refining co-thermal coupling hydrocarbon - Google Patents

Method for preparing high-added-value product by reforming light-driven carbonate refining co-thermal coupling hydrocarbon Download PDF

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CN115180593B
CN115180593B CN202210684268.6A CN202210684268A CN115180593B CN 115180593 B CN115180593 B CN 115180593B CN 202210684268 A CN202210684268 A CN 202210684268A CN 115180593 B CN115180593 B CN 115180593B
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carbonate
alkane
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gas
carbon dioxide
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CN115180593A (en
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赵宇飞
尹倩
沈天阳
李佳欣
宋宇飞
孔祥贵
段雪
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Beijing University of Chemical Technology
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    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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Abstract

The invention discloses a method for preparing high-added-value products by reforming carbonate refining co-thermal coupling hydrocarbons driven by light. The method is characterized in that carbonate is refined by alkane, and metal oxide can be obtained at a lower reaction temperature; the co-heat generated by the pyrolysis of the carbonate is utilized, and simultaneously, the carbon dioxide emitted in the pyrolysis process of the carbonate is utilized to carry out the co-heat coupling reforming of the alkane, so that a high added value product is obtained, the emission reduction of the carbon dioxide in the traditional carbonate refining process is realized, and the greenhouse effect is favorably relieved; compared with simple substance Ni catalyst, the catalyst drives the alkane reforming reaction under milder condition, reduces the thermodynamic energy barrier in the alkane reforming reaction, greatly improves the catalytic efficiency, avoids the excessive oxidation and deactivation of the catalyst, and is beneficial to reducing the energy consumption cost of the alkane dry reforming reaction. The invention can realize the aims of carbon emission reduction and energy consumption reduction and has wide application prospect.

Description

Method for preparing high-added-value product by reforming light-driven carbonate refining co-thermal coupling hydrocarbon
Technical Field
The invention belongs to the technical field of preparing metal oxide from carbonate, and particularly relates to a method for preparing high-added-value products by reforming light-driven carbonate refining co-thermal coupling hydrocarbons.
Background
The heavy process industries such as cement, steel, refractory materials, calcium carbide and the like are important supporting industries for the national economy development. Wherein carbonates are a common raw material required by the process industry, including limestone (CaCO) 3 ) Magnesite (MgCO) 3 ) Dolomite (CaMg (CO) 3 ) 2 ) And the like, and carbonate is subjected to high-temperature pyrolysis to form metal oxide, and the metal oxide is used as a basic raw material in national economy and can be subjected to subsequent production. However, carbonate pyrolysis emits a large amount of carbon dioxide, which is a heavy emission process, and the carbon dioxide emission amount of the related process industry exceeds 50% of the total national industrial carbon emission amount. How to convert and make available the carbon dioxide of the carbonate refining process in situ is a problem that is currently in need of solution in the carbonate refining industry. In addition, how to use clean energy sources such as light energy for traditional industry to further reduce production cost is of great significance. The solar-driven catalytic reaction has high selectivity under mild reaction conditions, which provides an alternative green sustainable development path for energy conversion and storage, and solves the problems of the current and futureOne of the more promising and practical solutions to the ball energy and environmental problems.
Disclosure of Invention
The invention provides a method for preparing high-added-value products by reforming light-driven carbonate refining co-thermal coupling hydrocarbons for reducing carbon dioxide emission, which aims to overcome the defect that a large amount of carbon dioxide is generated in the process of preparing oxides by decomposing traditional carbonates.
The method for preparing the high-added-value product by reforming the co-thermal coupling hydrocarbon through the carbonate refining driven by light comprises the following steps: placing a quartz tube in a photo-thermal reaction furnace, placing carbonate on the left side of the quartz tube, introducing alkane gas from an opening on the left side of the quartz tube, and heating and decomposing the carbonate in the alkane atmosphere to obtain solid metal oxide and carbon dioxide gas; and placing a catalyst on the right side of the quartz tube, applying light source irradiation above the catalyst, and carrying out photocatalytic reaction on alkane and carbon dioxide gas obtained by decomposing carbonate under the action of the catalyst to obtain high-added-value chemicals.
The quartz tube is contracted to 30-80% of the original tube diameter at the middle position of the left side where carbonate is placed and the right side where catalyst is placed.
The carbonate is any one or more of calcium carbonate, magnesium carbonate, iron carbonate, barium carbonate, cadmium carbonate, zinc carbonate, lead carbonate or copper carbonate.
The heating temperature of the carbonate in the alkane atmosphere is 300-800 ℃, the heating rate is 1-100 ℃/min, and the heating time is 1-200min.
The alkane gas is methane and/or ethane; the gas space velocity of alkane gas to carbonate is 10000-1000000 mL/g.h, and the pressure of alkane gas is normal pressure-10 MPa.
The alkane gas is doped with nitrogen or inert gas, and the doping amount is less than or equal to 99 percent.
The volume concentration of carbon dioxide is 1-50% when the alkane and carbon dioxide obtained by decomposing carbonate react under the action of a catalyst.
The light source is a xenon lamp or sunlight.
The illumination intensity of the light source is 0.1-100W/cm 2 。
The catalyst is a Ni-based monoatomic alloy catalyst.
The illumination conditions of the photocatalytic reaction are replaced by heating conditions.
The Ni-based monoatomic alloy catalyst also contains one or more noble metals Rh, ru, au, ag, pd; ni in a metal state is taken as an active component, noble metal is taken as an auxiliary agent, and a carrier is Al 2 O 3 、MgO、TiO 2 One or more of ZnO; the mass percentage content of Ni is 1-50%, and the mass percentage content of noble metal is 0.1-10%; the grain size of Ni is 3-15nm.
The preparation method of the Ni-based monoatomic alloy catalyst comprises the following steps: dissolving soluble nickel salt, soluble trivalent metal salt and soluble noble metal salt in CO-removing solution 2 Obtaining a mixed salt solution in water; dissolving sodium hydroxide in CO-removed solution 2 Obtaining an alkali solution in water; at N 2 Under the atmosphere, the mixed salt solution and the alkali solution are simultaneously added into deionized water in a dropwise manner, and the mixture is continuously stirred, so that the pH is controlled to be 8-12; stirring for 30-120 min after dripping, centrifuging the obtained mixture, and removing CO 2 Washing the precipitate with water until the supernatant pH is 7; and (3) rotary steaming, drying and grinding the obtained precipitate, and finally reducing and roasting in a reducing atmosphere.
The soluble trivalent metal salt is one or more of aluminum salt, ferric salt and cobalt salt.
The soluble noble metal salt is one or more of chloride salts of Rh, ru, au, ag, pd.
The dropping speed is 5-20rpm.
And after the dripping is finished, stirring is continued for 30-120 minutes, wherein the temperature is normal temperature to 60 ℃.
The temperature of the rotary steaming drying is 30-60 ℃, the vacuum degree is lower than-0.1 Mpa, and the rotary steaming is continued for 30-60 minutes after the precipitation drying.
The temperature of the reduction roasting is 400-800 ℃, the flow rate of the reducing gas is 20-100mL/min, and the temperature rising rate is 2-10 ℃/min.
The invention discloses a method for preparing high-added-value products by reforming light-driven carbonate refining co-thermal coupling hydrocarbons for reducing carbon dioxide emission, which is characterized in that the metal oxide of the carbonate is obtained at a lower reaction temperature by refining the carbonate with alkane; the co-heat generated by the pyrolysis of the carbonate is utilized, and simultaneously, the carbon dioxide emitted in the pyrolysis process of the carbonate is utilized to carry out the co-heat coupling reforming of the alkane, so that a high added value product is obtained, the emission reduction of the carbon dioxide in the traditional carbonate refining process is realized, and the greenhouse effect is favorably relieved; compared with simple substance Ni catalyst, the method drives the alkane reforming reaction under milder condition, reduces the thermodynamic energy barrier in the alkane reforming reaction, greatly improves the catalytic efficiency (5-6 times), avoids the excessive oxidation and deactivation of the catalyst, and is beneficial to reducing the energy consumption cost of the alkane dry reforming reaction process. The invention can realize the aims of carbon emission reduction and energy consumption reduction and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the process of optically driven carbonate refining co-thermally coupled methane reforming to make synthesis gas in example 1;
FIG. 2 is a scanning electron microscope image of magnesium carbonate in example 1;
FIG. 3 is a scanning electron microscope image of magnesium oxide after pyrolysis in example 1;
FIG. 4 is an X-ray diffraction pattern of magnesium carbonate and magnesium oxide after pyrolysis reaction of example 1;
FIG. 5 is a high resolution photograph of a RuNi monoatomic alloy of example 1;
FIG. 6 is a graph of the gas product performance results obtained with pure Ni and RuNi as catalysts in example 1;
FIG. 7 is a high resolution picture of AgNi monoatomic alloy;
FIG. 8 is a high resolution picture of RhNi monoatomic alloy;
FIG. 9 is a schematic diagram of the light driven carbonate refining co-thermally coupled ethane reforming process for ethylene in example 2;
FIG. 10 is a graph of gas chromatography of the gas product of example 2;
FIG. 11 is a schematic diagram of the process of the invention for photo-driven carbonate refining co-thermally coupled hydrocarbon reforming to produce high value-added products.
Detailed Description
Example 1
RuNi catalyst preparation: dissolving nickel chloride, aluminum chloride and ruthenium chloride in CO removal 2 Obtaining a mixed salt solution in water; dissolving sodium hydroxide in CO-removed solution 2 Obtaining an alkali solution in water; at N 2 Under the atmosphere, the mixed salt solution and the alkali solution are simultaneously added into deionized water in a dropwise manner, the dropping speed is 20rpm, and the mixture is continuously stirred at the same time, so that the pH is controlled to be 10; stirring at normal temperature for 100 min after dripping, centrifuging the obtained mixed solution, and removing CO 2 Washing the precipitate with water until the supernatant pH is 7; spin-evaporating the obtained precipitate at 60deg.C to dryness, vacuum degree lower than-0.1 Mpa, and spin-evaporating for 60 min after the precipitate is dried; grinding the precipitate, and finally reducing and roasting the precipitate at 400 ℃ under a hydrogen atmosphere, wherein the gas flow rate is 80mL/min, and the heating rate is 5 ℃/min. The Ni-based monoatomic RuNi alloy catalyst prepared by the method takes metallic Ni as an active component, ru as an auxiliary agent and Al as a carrier 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The mass percentage content of Ni is 1 percent, and the mass percentage content of noble metal is 0.1 percent.
As shown in fig. 1, the specific steps of the optically driven magnesium carbonate refining and co-thermally coupled methane reforming to produce synthesis gas are as follows: placing a quartz tube in a photo-thermal reaction furnace, and shrinking the tube diameter of the middle of the quartz tube to 50% of the original tube diameter; and (3) laying 100mg of magnesium carbonate on the left side of a closing opening in a quartz tube, laying 10mg of the prepared RuNi catalyst on the right side of the closing opening, flowing methane in from the left side opening of the quartz tube at a flow rate of 40mL/min, setting the pyrolysis temperature to 400 ℃, heating up for 30min, reacting for 90min, and roasting to obtain a magnesium oxide product. And (3) arranging a xenon lamp above the RuNi catalyst for irradiation, carrying out co-thermal coupling reforming on carbon dioxide obtained in the pyrolysis process of methane and magnesium carbonate under the action of RuNi monoatomic alloy, and carrying out online detection on a gas product by using a gas phase.
Fig. 2 is a scanning electron microscope image of magnesium carbonate, and fig. 3 is a scanning electron microscope image of magnesium oxide obtained after a pyrolysis reaction. As can be seen from the figure, magnesium carbonate before reaction is in the form of a bulk solid, in CH 4 Pyrolysis is carried out at 400 ℃ under atmosphere, and the obtained magnesium oxide is still a blocky solid. Self-contained in FIG. 4The lower two data lines are X-ray diffraction patterns of magnesium carbonate and magnesium oxide after pyrolysis reaction. Can be found in CH 4 After pyrolysis at 400 ℃ in the atmosphere, the magnesium carbonate is completely converted into magnesium oxide. Fig. 5 is a high resolution picture of the prepared RuNi monoatomic alloy catalyst with good Ru dispersion and Ni exposed (111) crystal planes. The performance results of the gas product obtained by coupling reforming are shown in FIG. 6, and the gas product is H 2 And CO, the addition of Ru greatly improves the yield of synthesis gas (by a factor of about 5-6) compared to the elemental Ni catalyst. Different noble metals such as Ag and Rh are doped in Ni-based catalyst to obtain different products (HCOOH and C 2 H 6 Etc.). Fig. 7 and 8 are high resolution pictures of AgNi and RhNi monoatomic alloys, respectively, with Ag or Rh well dispersed, and the alloys exposed the (111) crystal plane of Ni.
Example 2
As shown in fig. 9, the specific steps for reforming optically driven magnesium carbonate to co-thermally coupled ethane to ethylene are as follows: placing a quartz tube in a photo-thermal reaction furnace, and shrinking the tube diameter of the middle of the quartz tube to 50% of the original tube diameter; spreading 100mg of magnesium carbonate on the left side of a closing-in position in a quartz tube, spreading 10mg of RuNi catalyst on the right side of the closing-in position, setting the pyrolysis temperature at 400 ℃ and the heating time at 30min and the reaction time at 120 min, and roasting to obtain a magnesium oxide product; and (3) arranging a xenon lamp above the RuNi catalyst for irradiation, carrying out coupling reforming on ethane and carbon dioxide obtained in the pyrolysis process under the action of RuNi monoatomic alloy, and carrying out online detection on the product by using a gas phase. The detection result is shown in FIG. 10, and the gas product contains ethylene and a small amount of synthesis gas; the co-thermal coupling reforming of carbon dioxide produced by ethane and pyrolytic carbonate is illustrated to achieve the production of high value-added ethylene.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (7)

1. A method for preparing high-added-value products by reforming light-driven carbonate refining co-thermal coupling hydrocarbons, which is characterized by comprising the following steps: placing a quartz tube in a photo-thermal reaction furnace, placing carbonate on the left side of the quartz tube, introducing alkane gas from an opening on the left side of the quartz tube, and heating and decomposing the carbonate in the alkane atmosphere to obtain solid metal oxide and carbon dioxide gas; placing a catalyst on the right side of the quartz tube, applying light source irradiation above the catalyst, and carrying out photocatalytic reaction on alkane and carbon dioxide gas obtained by decomposing carbonate under the action of the catalyst to obtain chemicals with high added value;
the light source is a xenon lamp or sunlight; the illumination intensity of the light source is 0.1-100W/cm 2 ；
The catalyst is a Ni-based monoatomic alloy catalyst;
the Ni-based monoatomic alloy catalyst also contains one or more noble metals Rh, ru, au, ag, pd; ni in a metal state is taken as an active component, noble metal is taken as an auxiliary agent, and a carrier is Al 2 O 3 、MgO、TiO 2 One or more of ZnO; the mass percentage content of Ni is 1-50%, and the mass percentage content of noble metal is 0.1-10%; the grain size of Ni is 3-15nm.
2. The method of claim 1, wherein the quartz tube is contracted to 30-80% of the original tube diameter at the intermediate position of the left side of the carbonate and the right side of the catalyst.
3. The method of claim 1, wherein the carbonate is any one or more of calcium carbonate, magnesium carbonate, iron carbonate, barium carbonate, cadmium carbonate, zinc carbonate, lead carbonate, or copper carbonate; the heating temperature of the carbonate in the alkane atmosphere is 300-800 ℃, the heating rate is 1-100 ℃/min, and the heating time is 1-200min.
4. The method according to claim 1, wherein the alkane gas is methane and/or ethane; the gas space velocity of alkane gas to carbonate is 10000-1000000 mL/g.h, and the pressure of alkane gas is normal pressure-10 MPa; the volume concentration of carbon dioxide is 1-50% when the alkane and carbon dioxide obtained by decomposing carbonate react under the action of a catalyst.
5. The method according to claim 4, wherein the preparation method of the Ni-based monoatomic alloy catalyst comprises the following steps: dissolving soluble nickel salt, soluble trivalent metal salt and soluble noble metal salt in CO-removing solution 2 Obtaining a mixed salt solution in water; dissolving sodium hydroxide in CO-removed solution 2 Obtaining an alkali solution in water; at N 2 Under the atmosphere, the mixed salt solution and the alkali solution are simultaneously added into deionized water in a dropwise manner, and the mixture is continuously stirred, so that the pH is controlled to be 8-12; stirring for 30-120 min after dripping, centrifuging the obtained mixture, and removing CO 2 Washing the precipitate with water until the supernatant pH is 7; and (3) rotary steaming, drying and grinding the obtained precipitate, and finally reducing and roasting in a reducing atmosphere.
6. The method according to claim 5, wherein the soluble trivalent metal salt is one or more of aluminum salt, iron salt, cobalt salt; the soluble noble metal salt is one or more of chloride salts of Rh, ru, au, ag, pd.
7. The method according to claim 5, wherein the temperature of the reduction roasting is 400-800 ℃, the flow rate of the reducing gas is 20-100mL/min, and the temperature rising rate is 2-10 ℃/min.
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Citations (4)

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