CN112808276B - Preparation method and application method of catalyst for pyrolysis and pyrolysis of low-rank coal - Google Patents

Preparation method and application method of catalyst for pyrolysis and pyrolysis of low-rank coal Download PDF

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CN112808276B
CN112808276B CN202011629396.8A CN202011629396A CN112808276B CN 112808276 B CN112808276 B CN 112808276B CN 202011629396 A CN202011629396 A CN 202011629396A CN 112808276 B CN112808276 B CN 112808276B
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pyrolysis
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crox
coal
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CN112808276A (en
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陈吉浩
李悦
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Shaanxi Coalfield Geological Laboratory Test Co ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
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    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
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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
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Abstract

The invention discloses a preparation method of a catalyst for pyrolysis and cracking of low-rank coal, which comprises the steps of screening gamma-Al 2 O 3 A carrier; 2. cr (NO) 3 ) 3 Solution pair gamma-Al 2 O 3 Drying after dipping; 3. for gamma-Al after drying 2 O 3 Roasting to obtain CrOx/gamma-Al 2 O 3 A catalyst; 4. co (NO) 3 ) 3 Solution pair CrOx/gamma-Al 2 O 3 Soaking the catalyst and then airing; 5. for CrOx/gamma-Al after airing 2 O 3 Roasting to obtain Co-CrOx/gamma-Al 2 O 3 A catalyst; 6. by Fe (NO) 3 ) 3 Solution pair Co-CrOx/gamma-Al 2 O 3 Soaking the catalyst and then airing; 7. for Co-CrOx/gamma-Al after airing 2 And roasting the O3 catalyst to obtain a finished product. The invention also discloses a use method of the catalyst for pyrolysis and cracking of the low-rank coal. The catalyst prepared by the invention has high activity and good catalytic effect.

Description

Preparation method and application method of catalyst for pyrolysis and pyrolysis of low-rank coal
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and a use method of a catalyst for pyrolysis and cracking of low-rank coal.
Background
China belongs to the countries with oil deficiency and gas deficiency, and compared with the world energy structure, the petroleum and natural gas resources of China are seriously deficient, so that coal plays a core role in the process of rapidly increasing Chinese economy. However, serious environmental pollution and damage are brought by coal development, meanwhile, the comprehensive utilization rate of coal resources is low, and the deep processing core technology of coal is weak. Although China has made great progress in the field of coal chemical industry, the products of China coal chemical industry still take primary coke as main products, and core technology is still lacking; the coal cleaning technology is developed, the comprehensive utilization efficiency and clean utilization level of coal are improved, the sustainable development of energy is realized, and the method has important significance for the sustainable development of China in the future.
Coal pyrolysis refers to a thermal processing process for converting solid coal into liquid (coal tar and chemicals), gas and solid semicoke under relatively mild conditions, and is an important coal quality utilization technology, and is a technology and necessary steps for preparing light tar and fuel gas from coal. The existing catalyst for preparing tar and generating fuel gas by pyrolysis and pyrolysis of coal can only aim at increasing the yield or quality of certain pyrolysis products in the pyrolysis and catalytic pyrolysis process of coal, has low catalytic activity, is easy to accumulate carbon on the surface of the catalyst, is difficult to reactivate after deactivation, and has low recycling rate; and the existing catalysts are relatively expensive.
The low-rank coal is coal with longer flame and smoke during combustion, and has low coalification degree, and most of bituminous coal belongs to the low-rank coal. The existing catalyst used for pyrolysis and pyrolysis of low-rank coal also mainly has the problems of low catalytic pyrolysis efficiency, easy deactivation, difficult reactivation and inapplicability to industrial application.
γ-Al 2 O 3 (gamma aluminum oxide, also called activated alumina) is very suitable for experimental operation and industrial application due to its excellent physical and chemical properties, and has a high specific surface area suitable for use as a carrier for preparing a catalyst, while being gamma-Al 2 O 3 The catalyst prepared by the carrier can be repeatedly utilized after being activated, so that the production cost is reduced, and the catalyst is applied to a pyrolysis cracking process of coal, thereby realizing the recycling of resources. For this purpose, how to pass gamma-Al 2 O 3 The preparation of catalysts for the pyrolysis catalytic pyrolysis of coal to produce coal tar and fuel gas is one of the key points of the study of the person skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a catalyst for pyrolysis and cracking of low-rank coal, which uses gamma-Al 2 O 3 The catalyst prepared by the carrier is used for carrying out pyrolysis catalytic pyrolysis on the bituminous coal, so that the yield of tar and fuel gas of the bituminous coal is improved, and the prepared catalyst has high activity and good catalytic effect.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the catalyst for pyrolysis and pyrolysis of the low-rank coal is characterized by comprising the following steps of:
step one, screening spherical gamma-Al with the particle size of 3-5 mm 2 O 3 As a support for the catalyst;
step two, preparing Cr (NO) with mass fraction of 3% -11% 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in a muffle furnace for 2-4 h at 400-550 deg.c to obtain Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, co (NO) with mass fraction of 3-11% is configured 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2-4 h at 400-550 ℃ to obtain the catalyst containing Co 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 3% -11% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2-4 h at 400-550 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: the spherical gamma-Al in the step one 2 O 3 Has a screening particle size of 4mm, and Cr (NO 3 ) 3 The mass fraction of the solution was 8%.
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: and in the third step, the roasting time of the muffle furnace is 4 hours, and the roasting temperature is 450 ℃.
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: co (NO) as described in step four 3 ) 3 The mass fraction of the solution is 8%, the roasting time of the muffle furnace in the fifth step is 4 hours, and the roasting temperature is 450 ℃.
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: fe (NO) as described in step six 3 ) 3 The mass fraction of the solution is 5%, the roasting time of the muffle furnace in the step seven is 4 hours, and the roasting temperature is 450 ℃.
In addition, the invention also provides a use method of the catalyst for pyrolysis and pyrolysis of low-rank coal, which is characterized in that: the using method is that a coal sample and the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of the low-rank coal prepared by the method of claim 1 are subjected to 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:3 to the maximum10, the pyrolysis and cracking temperature of the coal sample is 600-700 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The catalyst is put into the coal pyrolysis catalytic system to repeat the coal pyrolysis catalytic pyrolysis reaction for 1 to 4 times, and then the pyrolysis deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the roasting time is 2-4 h, and the roasting temperature is 400-550 ℃.
The application method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:5, the pyrolysis and pyrolysis temperature of the coal sample is 650 ℃; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The catalyst was repeated 3 times, the cracking deactivated Fe-Co-CrOx/gamma-Al 2 O 3 The time for roasting and regenerating the catalyst is 3 hours, and the temperature for roasting and regenerating is 450 ℃.
The application method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: the coal pyrolysis cracking catalytic system comprises a coal tar device, wherein the coal tar device comprises a high-temperature pyrolysis furnace, a quartz tube with a branch pipe, a first conical flask, an ice water bath pot, a first conveying pipe, a dryer, a second conveying pipe, a mass flowmeter, a third conveying pipe and a gas collecting bag, one end of a main pipe with the quartz tube with the branch pipe is closed, the other end of the main pipe is open, a branch pipe with the quartz tube with the branch pipe is close to the open end, a porcelain boat is placed in the closed end of the quartz tube with the branch pipe, the closed end of the quartz tube with the branch pipe extends into the high-temperature pyrolysis furnace, and a bottle rubber plug is arranged at the open end of the quartz tube with the branch pipe; the lower part of the first conical flask is positioned in an ice water bath kettle, an ice water mixture is filled in the ice water bath kettle, a first flask rubber plug is arranged at the bottle mouth of the first conical flask, a tar absorbent is filled in the first conical flask, a branch pipe penetrates through the first flask rubber plug, the pipe orifice is positioned below the liquid level of the tar absorbent, one end of a first conveying pipe is inserted into the first conical flask from the first flask rubber plug, the pipe orifice of the first conveying pipe is positioned above the liquid level of the tar absorbent, the other end of the first conveying pipe is connected with an inlet of a dryer, an outlet of the dryer is connected with one end of a second conveying pipe, the other end of the second conveying pipe is connected with an inlet of a mass flowmeter, the other end of the mass flowmeter is connected with one end of a third conveying pipe, the other end of the third conveying pipe is connected with an inlet of a gas collecting bag, and a valve is arranged on the third conveying pipe.
The application method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: the device comprises a first conical bottle, a first oil water measuring device, a second conical bottle and a universal electric furnace, wherein the first conical bottle is used for measuring the water quality of an absorbent mixture after tar absorption in the first conical bottle, the first oil water measuring device comprises a condensation return pipe, a water measuring instrument, the second conical bottle and the universal electric furnace, the second conical bottle is arranged on the universal electric furnace and is heated, the tar absorbent mixture after tar absorption is contained in the second conical bottle, a second bottle rubber plug is arranged on the bottle mouth of the second conical bottle, the condensation return pipe is located above the universal electric furnace, the water measuring instrument is arranged at the lower end of the condensation return pipe, a cold water inlet is formed in one side of the lower part of the condensation return pipe, a cold water outlet is formed in one side of the upper part of the condensation return pipe, a branch pipe of the water measuring instrument is inserted into the second conical bottle from the second bottle rubber plug, and a pipe orifice of the branch pipe of the water measuring instrument is located above the liquid level of the absorbent mixture after tar absorption.
The application method of the catalyst for pyrolysis and pyrolysis of low-rank coal is characterized by comprising the following steps of: the sealed end of the quartz tube with the branch pipe horizontally extends into the pyrolysis furnace, the heating temperature of the universal electric furnace on the second conical bottle is 100-150 ℃, and the heating temperature of the pyrolysis furnace on the sealed end of the quartz tube with the branch pipe is 450-850 ℃.
Compared with the prior art, the invention has the following advantages:
1. the Fe-Co-CrOx/gamma-Al prepared by the invention 2 O 3 The catalyst is suitable for the pyrolysis and pyrolysis process of low-rank coal, can greatly improve the pyrolysis and pyrolysis efficiency of the low-rank coal, improves the yield of pyrolysis gas and the contents of hydrogen and methane in the pyrolysis gas, and simultaneously increases the yield of tar and improves the quality of tar.
2. The invention uses gamma-Al 2 O 3 As a carrier of the catalyst, the catalyst has excellent physical and chemical properties and mechanical properties, and Fe-Co-CrOx/gamma-Al is prepared by adopting a muffle furnace roasting mode 2 O 3 The catalyst has simple preparation process and is suitable for industrial production application.
3. The invention adopts an isovolumetric impregnation method to gradually load Cr 2 O 3 、Co 2 O 3 And Fe (Fe) 2 O 3 Three metal oxides, can solve the problem of Cr caused by simultaneous impregnation 2 O 3 、Co 2 O 3 And Fe (Fe) 2 O 3 The problem of reducing the cracking effect of the catalyst due to competitive adsorption is solved, so that the loading capacity reaches the optimal loading effect, and the Fe-Co-CrOx/gamma-Al is prepared 2 O 3 The catalyst achieves the best catalytic effect.
4. The Fe-Co-CrOx/gamma-Al prepared by the invention 2 O 3 The catalyst has the characteristics of high activity, strong selectivity and long service life, and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 The catalyst can reach a higher pyrolysis cracking effect again through the roasting of the muffle furnace, so that the recycling of the catalyst is realized, and the catalyst is suitable for industrial application.
In conclusion, the invention uses gamma-Al 2 O 3 The catalyst is a carrier, and the mechanical property and the physical property of the catalyst are improved; the coal and the catalyst are subjected to mixed pyrolysis cracking, so that the oil yield and the gas yield of the coal are improved, and the contents of hydrogen and methane in the gas are improved; the prepared catalyst has high activity, and the deactivated catalyst can be activated and regenerated, so that the recycling of the catalyst is realized.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
Fig. 1 is a schematic structural view of the present invention.
FIG. 2 is a schematic diagram of the coal tar system of the present invention.
FIG. 3 is a schematic diagram of the device for measuring the moisture in oil according to the present invention.
FIG. 4 shows γ -Al in step one of the present invention 2 O 3 XRD spectrum of the carrier.
FIG. 5 shows CrOx/gamma-Al in step three of the present invention 2 O 3 XRD spectrum of the catalyst.
FIG. 6 is a chart showing Co-CrOx/gamma-Al in step five of the present invention 2 O 3 XRD spectrum of the catalyst.
FIG. 7 is a schematic diagram of Fe-Co-CrOx/gamma-Al in step seven of the present invention 2 O 3 XRD spectrum of the catalyst.
Reference numerals illustrate:
1-a high-temperature pyrolysis furnace; 2-a porcelain boat; 3-quartz tube with branch tube;
3-1 branch pipes; 3-2-bottle rubber stopper; 4-a first conical flask;
4-1 to a first bottle rubber stopper; 5-tar absorbent; 5-1-absorbing the tar and then absorbing the mixture of the absorbent;
6-an ice water bath pan; 7-an ice-water mixture; 8-a first conveying pipe;
9-a dryer; 10-a second conveying pipe; 11-a mass flowmeter;
12-a third conveying pipe; 13-a valve; 14-an air collecting bag;
15-condensing reflux pipe; 15-1-a cold water inlet; 15-2-a cold water outlet;
16-a moisture meter; 17-a second conical flask; 17-1-a second bottle rubber stopper;
18-universal electric furnace.
Detailed Description
Example 1
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal in the embodiment comprises the following steps:
step one, screening spherical gamma-Al with the particle size of 3mm 2 O 3 As a support for the catalyst;
step two, configuring Cr (NO) with mass fraction of 3% 3 ) 3 The solution (i.e. chromium nitrate solution) adopts an isovolumetric impregnation method to carry out the gamma-Al process in the step one 2 O 3 Soaking the carrier for 24h at room temperature, and takingTaking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in a muffle furnace for 3h at 550 ℃ to obtain the Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, configuring Co (NO) with mass fraction of 6% 3 ) 3 The solution (cobalt nitrate solution) is subjected to an isovolumetric impregnation method to obtain the solution containing Cr 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 4h at 450 ℃ to obtain Co-containing catalyst 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 5% 3 ) 3 The solution (namely ferric nitrate solution) is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 4h at 550 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
The application method of the catalyst for pyrolysis and pyrolysis of the low-rank coal in the embodiment comprises the following steps: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of coal sample and low-rank coal prepared by the method 2 O 3 The catalyst is put into a porcelain boat of a coal pyrolysis cracking catalytic system together, and coal heat is generated in a quartz tube with a branch pipe, which is used for placing the porcelain boatThe pyrolysis reaction is catalyzed, and tar gas generated by pyrolysis and catalytic pyrolysis of coal enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:5, and the pyrolysis and pyrolysis temperature of the coal sample is 650 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 After the catalyst is put into the coal pyrolysis catalytic cracking system for repeating the coal pyrolysis catalytic cracking reaction for 4 times, the cracked and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the calcination time was 2 hours and the calcination temperature was 550 ℃.
As shown in fig. 1 and 2, in this embodiment, the pyrolysis catalytic system for coal comprises a coal tar device, the coal tar device comprises a high-temperature pyrolysis furnace 1, a quartz tube with branch pipes 3, a first conical flask 4, an ice water bath 6, a first conveying pipe 8, a dryer 9, a second conveying pipe 10, a mass flowmeter 11, a third conveying pipe 12 and a gas collecting bag 14, one end of a main pipe with branch pipes 3 is closed, the other end of the main pipe with branch pipes is open, a branch pipe 3-1 with branch pipes 3 is arranged near the open end, a porcelain boat 2 is placed in the closed end of the quartz tube with branch pipes 3, the closed end of the quartz tube with branch pipes 3 extends into the high-temperature pyrolysis furnace 1, and a bottle rubber plug 3-2 is arranged at the open end of the quartz tube with branch pipes 3; the lower part of the first conical flask 4 is positioned in the ice water bath 6, the ice water bath 6 is internally filled with an ice water mixture 7, the bottleneck of the first conical flask 4 is provided with a first flask rubber plug 4-1, the first conical flask 4 is internally filled with a tar absorbent 5, the branch pipe 3-1 penetrates through the first flask rubber plug 4-1, the pipe orifice is positioned below the liquid level of the tar absorbent 5, one end of the first conveying pipe 8 is inserted into the first conical flask 4 from the first flask rubber plug 4-1, the pipe orifice of the first conveying pipe 8 is positioned above the liquid level of the tar absorbent 5, the other end of the first conveying pipe 8 is connected with the inlet of the dryer 9, the outlet of the dryer 9 is connected with one end of the second conveying pipe 10, the other end of the second conveying pipe 10 is connected with the inlet of the mass flowmeter 11, the other end of the mass flowmeter 11 is connected with one end of the third conveying pipe 12, the other end of the third conveying pipe 12 is connected with the inlet of the collector 14, and the valve 13 is arranged on the third conveying pipe 12.
As shown in fig. 1 and 3, the coal tar device in this embodiment further includes an in-oil moisture measuring device for measuring the moisture mass in the absorbent mixture 5-1 after absorbing tar in the first conical flask 4, the in-oil moisture measuring device includes a condensation return pipe 15, a moisture measuring apparatus 16, a second conical flask 17 and a universal electric furnace 18, the second conical flask 17 is arranged on the universal electric furnace 18 and heated, the second conical flask 17 contains the absorbent mixture 5-1 after absorbing tar, a mouth of the second conical flask 17 is provided with a second flask rubber plug 17-1, the condensation return pipe 15 is located above the universal electric furnace 18, the moisture measuring apparatus 16 is installed at a lower end of the condensation return pipe 15, a cold water inlet 15-1 is arranged at a lower side of the condensation return pipe 15, a cold water outlet 15-2 is arranged at an upper side of the condensation return pipe 15, a branch pipe of the moisture measuring apparatus 16 is inserted into the second conical flask 17 from the second conical flask rubber plug 17-1, and a branch pipe of the moisture measuring apparatus 16 is located above the absorbent mixture after absorbing tar 5-1.
The coal pyrolysis cracking catalytic system is provided with a coal tar device and an oil moisture measuring device, namely, the pyrolysis oil extraction process and the tar purification process are carried out separately, so that the yield of tar is improved, the moisture of the tar is separated out to purify the tar, and the tar purity is high. The coal sample is pyrolyzed by the high-temperature pyrolysis furnace, the coal sample and the catalyst are contained in the porcelain boat, and the produced tar gas is directly absorbed and collected by the absorbent, so that the tar is effectively prevented from condensing in a pipeline, the loss of the tar is reduced, the yield and the quality of the tar are improved, and the combustible pyrolysis gas in the tar is purified and collected. In the device for measuring the moisture in the oil, the moisture in the tar is separated and accurately measured by utilizing the modes of distillation and condensation reflux, so that the moisture content of the tar is measured, and the purification of tar is realized.
In this embodiment, the closed end of the quartz tube with branch pipe 3 horizontally extends into the high-temperature pyrolysis furnace 1, the heating temperature of the universal electric furnace 18 to the second conical bottle 17 is 100 ℃ to 150 ℃, and the heating temperature of the high-temperature pyrolysis furnace 1 to the closed end of the quartz tube with branch pipe 3 is 450 ℃ to 850 ℃.
In this embodiment, the volume of the tar absorbent 5 contained in the first conical flask 4 is 1/3 of the volume of the first conical flask 4.
In this embodiment, the tar absorbent 5 is gasoline, and the desiccant filled in the dryer 9 is a silica gel desiccant.
In this embodiment, the working principle of the pyrolysis catalytic system for coal pyrolysis is as follows: the porcelain boat 2 is placed in the quartz tube 3 with the branch pipes, the coal sample ag and the catalyst mass bg are added into the porcelain boat 2, and the quartz tube 3 with the branch pipes stretches into the high-temperature pyrolysis furnace 1 to raise the temperature to 650 ℃. Tar gas generated by pyrolysis (the pyrolysis process is accompanied by pyrolysis) enters the first conical flask 4, tar and moisture are absorbed by the tar absorbent 5 in the first conical flask 4, the generated gas enters the dryer 9 through the first conveying pipe 8 to be dried, the volume of the generated gas is recorded by the mass flowmeter 11, and the generated gas enters the gas collecting bag 14 to be collected by opening the valve 13. Wherein the mass ratio of the coal sample a to the catalyst mass b is 1:3-10.
Pouring the absorbent mixture 5-1 after absorbing tar in the first conical flask 4 into the second conical flask 17, condensing the water discharged from the upper end of cold water in the lower end of the condensing return pipe 15, setting the temperature of the universal electric furnace 18 to be 100-150 ℃, distilling for 60 minutes, and recording the quality of produced water by the moisture measuring instrument 16 when the produced moisture enters the moisture measuring instrument 16, and calculating the oil yield of the coal sample according to the quality of the water to obtain the tar with higher purity.
Example 2
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal in the embodiment comprises the following steps:
step one, screening spherical gamma-Al with the particle size of 5mm 2 O 3 As a support for the catalyst;
step two, configuring Cr (NO) with mass fraction of 11% 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in muffle furnace for 4 hr at 400 deg.C to obtain Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, configuring Co (NO) with mass fraction of 3% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2h at 550 ℃ to obtain Co-containing catalyst 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 8% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 4 hours at 400 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
The application method of the catalyst for pyrolysis and pyrolysis of the low-rank coal in the embodiment comprises the following steps: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of coal sample and low-rank coal prepared by the method 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:3, and the pyrolysis and pyrolysis temperature of the coal sample is 650 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 After the catalyst is put into the coal pyrolysis catalytic cracking system and is repeated for 2 times, the cracked and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the calcination time was 2 hours and the calcination temperature was 450 ℃.
In this embodiment, the structure, connection relationship, and operation principle of the rest are the same as those of embodiment 1.
Example 3
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal in the embodiment comprises the following steps:
step one, screening spherical gamma-Al with the particle size of 4mm 2 O 3 As a support for the catalyst;
step two, configuring Cr (NO) with mass fraction of 5% 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in muffle furnace for 4 hr at 450 deg.C to obtain Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, configuring Co (NO) with mass fraction of 10 percent 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 4 hours at 500 ℃ to obtain Co-containing catalyst 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 3% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2h at 460 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
The application method of the catalyst for pyrolysis and pyrolysis of the low-rank coal in the embodiment comprises the following steps: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of coal sample and low-rank coal prepared by the method 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:10, and the pyrolysis and pyrolysis temperature of the coal sample is 680 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 After the catalyst is put into the coal pyrolysis catalytic cracking system and is repeated for 3 times, the cracked and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the roasting time is 3.5h, and the roasting temperature is 450 ℃.
In this embodiment, the structure, connection relationship, and operation principle of the rest are the same as those of embodiment 1.
Example 4
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal in the embodiment comprises the following steps:
step one, screening spherical gamma-Al with the particle size of 4mm 2 O 3 As a support for the catalyst;
step two, preparing Cr (NO) with mass fraction of 8 percent 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in muffle furnace for 2 hr at 500 deg.C to obtain Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, configuring Co (NO) with mass fraction of 11% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 3h at 450 ℃ to obtain Co-containing catalyst 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 5% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 3h at 500 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
Application method of catalyst for pyrolysis and pyrolysis of low-rank coal in embodimentThe method comprises the following steps: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of coal sample and low-rank coal prepared by the method 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:6, and the pyrolysis and pyrolysis temperature of the coal sample is 600 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 After the catalyst is put into the coal pyrolysis catalytic cracking system and the coal pyrolysis catalytic cracking reaction is repeated for 1 time, the cracked and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the calcination time was 3 hours and the calcination temperature was 400 ℃.
In this embodiment, the structure, connection relationship, and operation principle of the rest are the same as those of embodiment 1.
Example 5
The preparation method of the catalyst for pyrolysis and pyrolysis of low-rank coal in the embodiment comprises the following steps:
step one, screening spherical gamma-Al with the particle size of 3mm 2 O 3 As a support for the catalyst;
step two, configuring Cr (NO) with mass fraction of 10 percent 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in a muffle furnace for 3h at 400 ℃ to obtain the Cr-containing alloy 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, configuring Co (NO) with mass fraction of 8% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking catalyst at room temperature for 24 hrTaking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2h at 400 ℃ to obtain Co-containing catalyst 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with the mass fraction of 11 percent 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2.5h at 450 ℃ to obtain the Fe-containing catalyst 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
The application method of the catalyst for pyrolysis and pyrolysis of the low-rank coal in the embodiment comprises the following steps: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of coal sample and low-rank coal prepared by the method 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:8, and the pyrolysis and pyrolysis temperature of the coal sample is 700 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 After the catalyst is put into the coal pyrolysis catalytic cracking system for repeating the coal pyrolysis catalytic cracking reaction for 4 times, the cracked and deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the calcination time was 4 hours and the calcination temperature was 500 ℃.
In this embodiment, the structure, connection relationship, and operation principle of the rest are the same as those of embodiment 1.
In examples 1 to 5, all of them were gamma-Al 2 O 3 As a carrier of the catalyst, the catalyst for pyrolysis and pyrolysis of low-rank coal, namely Fe-Co-CrOx/gamma-Al, is prepared through repeated isovolumetric impregnation and muffle furnace roasting processes 2 O 3 The catalyst is mainly suitable for the pyrolysis and cracking process of low-rank coal.
FIG. 4 shows the process of the present invention from gamma-Al in steps three, five and six 2 O 3 Preparation of CrOx/gamma-Al support 2 O 3 、 Co-CrOx/γ-Al 2 O 3 And Fe-Co-CrOx/gamma-Al 2 O 3 Catalyst and gamma-Al 2 O 3 Is a XRD spectrum of (C).
FIG. 4 shows γ -Al in step one of the present invention 2 O 3 XRD spectrum of the carrier. In fig. 4, 2θ angles of 32.78 °, 36.54 °, 37.51 °, 43.17 °, 45.79 °, 66.76 ° and 67.31 ° are characteristic peaks of γ -Al2O3, and the crystal structure is obvious, so that a stronger active site can be generated.
FIG. 5 shows CrOx/gamma-Al in step three of the present invention 2 O 3 XRD spectrum of the catalyst. Is prepared into CrOx/gamma-Al through load roasting 2 O 3 Catalyst, formed of different metal oxides Cr 2 O 3 CrO and CrO 3 In FIG. 5 Cr 2 O 3 The 2 theta angles of the corresponding characteristic peaks are 24.49 degrees, 33.60 degrees, 36.20 degrees, 41.48 degrees, 50.22 degrees and 54.85 degrees, the 2 theta angles of the corresponding characteristic peaks of CrO are 34.60 degrees, 30.27 degrees, 43.25 degrees, 57.17 degrees and 62.82 degrees, and the 2 theta angles of CrO are 34.60 degrees, 30.27 degrees, 43.25 degrees, 57.17 degrees and 62.82 degrees 3 The 2 theta angles of the corresponding characteristic peaks are 21.19 degrees, 25.92 degrees and 26.32 degrees, and CrOx/gamma-Al is roasted 2 O 3 The active components generated by the catalyst are obviously increased, and the dispersibility is good, so that CrOx/gamma-Al 2 O 3 The catalyst activity is increased.
FIG. 6 is a chart showing Co-CrOx/gamma-Al in step five of the present invention 2 O 3 XRD spectrum of the catalyst. The Co-CrOx/gamma-Al is prepared by load roasting 2 O 3 Catalyst, further increase Co formation 2 O 3 And CoO, co in FIG. 6 2 O 3 The 2 theta angles of the corresponding characteristic peaks are 27.77 degrees, 31.14 degrees, 38.61 degrees, 51.28 degrees, 56.40 degrees, 58.76 degrees and 67.31 degrees, coO, and the 2 theta angles of the corresponding characteristic peaks are 36.49 degrees, 34.15 degrees, 42.39 degrees, 57.30 degrees and 61.52 degrees, and the Co-CrOx/gamma-Al is roasted 2 O 3 The catalyst further increases Co 2 O 3 And CoO production, and good dispersibility, so that Co-CrOx/gamma-Al 2 O 3 The catalyst activity is further increased.
FIG. 7 is a schematic diagram of Fe-Co-CrOx/gamma-Al in step seven of the present invention 2 O 3 XRD spectrum of the catalyst. The Fe-Co-CrOx/gamma-Al is prepared by load roasting 2 O 3 Catalyst, further increase Fe 2 O 3 And FeO, fe in FIG. 7 2 O 3 The 2 theta angles of the corresponding characteristic peaks are 14.73 degrees, 20.35 degrees, 24.71 degrees, 29.76 degrees, 32.78 degrees, 35.68 degrees, 33.82 degrees, 38.10 degrees, 54.94 degrees and 70.18 degrees, and the 2 theta angles of the FeO corresponding characteristic peaks are 36.04 degrees, 41.93 degrees, 60.76 degrees, 73.13 degrees and 76.99 degrees, and the Fe-Co-CrOx/gamma-Al is roasted 2 O 3 The catalyst further increases Fe 2 O 3 And FeO production, and good dispersibility, so that Fe-Co-CrOx/gamma-Al 2 O 3 The catalyst activity is further increased.
The intermediate Fe-Co-CrOx/gamma-Al of examples 1 to 5 of the present invention was used 2 O 3 The catalyst is used for preparing tar and gas by catalytic pyrolysis and cracking of bituminous coal (low-rank coal), and the catalytic pyrolysis and cracking data of the bituminous coal are shown in the following table under the condition of the same other parameters.
The total gas mass being the mass of all gases produced, mainly O 2 、N 2 、CO 2 、CO、 H 2 、CH 4 、C 2 Etc., containing a fuel gas; the fuel gas is mainly CO and H 2 、CH 4 The heat providing gas can be combusted.
Table 1 table of conditions of catalytic pyrolysis cracking of bituminous coal
Figure RE-GDA0002987597710000161
As can be seen from Table 1, the mass of tar produced by direct pyrolysis of 15g of bituminous coal without catalyst was 1.224g, the total gas mass was 1.44g, and the fuel gas content was 46% (as detected by gas chromatography). When gamma-Al is directly used 2 O 3 When used as a catalyst, the mass of tar was increased, the mass of tar was 1.428g, and the fuel gas content was 52%, indicating gamma-Al 2 O 3 The yields of tar and total gases are increased and the fuel gas content in the pyrolysis gases is increased.
When the Fe-Co-CrOx/gamma-Al prepared by the invention is added 2 O 3 When the catalyst is used, the mass yield of tar is further increased to 1.926g; the total gas quality is further improved to 2.41g; the fuel gas content in the gas reaches 89%.
It can be seen that the Fe-Co-CrOx/gamma-Al prepared by the invention 2 O 3 The catalyst can lead the bituminous coal to produce more tar and gas in the pyrolysis process, and the fuel gas content in the gas is greatly improved; compared with the raw bituminous coal (without catalyst), the tar yield is improved by 57%, the total gas yield is improved by 67%, and the fuel gas content is improved by 93%, so that the catalyst prepared by the invention has good catalytic effect.
In addition, when Fe-Co-CrOx/gamma-Al after regeneration and activation is added 2 O 3 When the catalyst is used, the mass of the generated tar is 1.783, the total gas mass is 2.38, the fuel gas content is 86, and the catalyst is matched with the Fe-Co-CrOx/gamma-Al prepared by the invention 2 O 3 The effect of the catalyst (non-regenerated and activated) is basically similar, and it can be seen that Fe-Co-CrOx/gamma-Al after regenerated and activated 2 O 3 The catalytic pyrolysis cracking effect of the catalyst is also good.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (10)

1. The preparation method of the catalyst for pyrolysis and pyrolysis of the low-rank coal is characterized by comprising the following steps of:
step one, screening spherical gamma-Al with the particle size of 3-5 mm 2 O 3 As a support for the catalyst;
step two, preparing Cr (NO) with mass fraction of 3% -11% 3 ) 3 Solution, adopting an isovolumetric impregnation method to carry out the gamma-Al in the first step 2 O 3 Soaking the carrier for 24 hours at room temperature, taking out and airing;
step three, dipping and airing the gamma-Al in the step two 2 O 3 Roasting in a muffle furnace for 2-4 h at 400-550 deg.c to obtain Cr-containing material 2 O 3 CrOx/gamma-Al of active component 2 O 3 A catalyst;
step four, co (NO) with mass fraction of 3-11% is configured 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Cr-containing solution in the step three 2 O 3 CrOx/gamma-Al of active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step five, soaking and airing the Cr-containing material in the step four 2 O 3 CrOx/gamma-Al of active component 2 O 3 Placing the catalyst in a muffle furnace for roasting for 2-4 h at 400-550 ℃ to obtain the catalyst containing Co 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 A catalyst;
step six, preparing Fe (NO) with mass fraction of 3% -11% 3 ) 3 The solution is prepared by adopting an isovolumetric impregnation method to obtain the Co-containing solution in the step five 2 O 3 Co-CrOx/gamma-Al as active component 2 O 3 Soaking the catalyst for 24 hours at room temperature, taking out and airing;
step seven, dipping and airing the Co-containing material in the step six 2 O 3 Active component Co-CrOx/gamma-Al 2 O 3 The catalyst is placed in a muffle furnace for roasting for 2-4 h, the roasting temperature is 400-550 ℃,to obtain Fe-containing alloy 2 O 3 Fe-Co-CrOx/gamma-Al as active component 2 O 3 The catalyst is finally prepared into the Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 A catalyst.
2. The method for preparing the catalyst for pyrolysis and pyrolysis of low-rank coal according to claim 1, wherein the method comprises the following steps: the spherical gamma-Al in the step one 2 O 3 Has a screening particle size of 4mm, and Cr (NO 3 ) 3 The mass fraction of the solution was 8%.
3. The method for preparing the catalyst for pyrolysis and pyrolysis of low-rank coal according to claim 1, wherein the method comprises the following steps: and in the third step, the roasting time of the muffle furnace is 4 hours, and the roasting temperature is 450 ℃.
4. The method for preparing the catalyst for pyrolysis and pyrolysis of low-rank coal according to claim 1, wherein the method comprises the following steps: co (NO) as described in step four 3 ) 3 The mass fraction of the solution is 8%, the roasting time of the muffle furnace in the fifth step is 4 hours, and the roasting temperature is 450 ℃.
5. The method for preparing the catalyst for pyrolysis and pyrolysis of low-rank coal according to claim 1, wherein the method comprises the following steps: fe (NO) as described in step six 3 ) 3 The mass fraction of the solution is 5%, the roasting time of the muffle furnace in the step seven is 4 hours, and the roasting temperature is 450 ℃.
6. The method for using the catalyst for pyrolysis and cracking of the low-rank coal, which is prepared by the method according to claim 1, is characterized in that: the using method is that the coal sample and the low-rank coal are pyrolyzed and cracked by Fe-Co-CrOx/gamma-Al 2 O 3 The catalyst is placed in a porcelain boat of a coal pyrolysis cracking catalytic system together, a coal pyrolysis catalytic cracking reaction occurs in a quartz tube with a branch pipe, which is placed in the porcelain boat, and tar gas generated by the coal pyrolysis catalytic cracking enters a first conical flask; fe-Co-CrOx/gamma for pyrolysis and pyrolysis of low-rank coal-Al 2 O 3 The mass ratio of the catalyst to the coal sample is 1:3-10, and the pyrolysis and pyrolysis temperature of the coal sample is 600-700 ℃;
Fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The catalyst is put into the coal pyrolysis catalytic system to repeat the coal pyrolysis catalytic pyrolysis reaction for 1 to 4 times, and then the pyrolysis deactivated Fe-Co-CrOx/gamma-Al 2 O 3 Placing the catalyst in a muffle furnace for roasting and regenerating; the roasting time is 2-4 h, and the roasting temperature is 400-550 ℃.
7. The method for using the catalyst for pyrolysis and cracking of low-rank coal according to claim 6, wherein: fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The mass ratio of the catalyst to the coal sample is 1:5, the pyrolysis and pyrolysis temperature of the coal sample is 650 ℃; fe-Co-CrOx/gamma-Al for pyrolysis and pyrolysis of low-rank coal 2 O 3 The catalyst was repeated 3 times, the cracking deactivated Fe-Co-CrOx/gamma-Al 2 O 3 The time for roasting and regenerating the catalyst is 3 hours, and the temperature for roasting and regenerating is 450 ℃.
8. The method for using the catalyst for pyrolysis and cracking of low-rank coal according to claim 6, wherein: the coal pyrolysis cracking catalytic system comprises a coal tar device, the coal tar device comprises a high-temperature pyrolysis furnace (1), a quartz tube with a branch tube (3), a first conical flask (4), an ice water bath pot (6), a first conveying tube (8), a dryer (9), a second conveying tube (10), a mass flowmeter (11), a third conveying tube (12) and an air collecting bag (14), one end of a main tube with the quartz tube (3) is closed, the other end of the main tube with the quartz tube is open, a branch tube (3-1) with the quartz tube (3) is close to the open end, a porcelain boat (2) is placed in the closed end of the quartz tube with the branch tube (3), the closed end of the quartz tube with the branch tube (3) stretches into the high-temperature pyrolysis furnace (1), and a bottle rubber plug (3-2) is arranged at the open end of the quartz tube with the branch tube (3); the ice water kettle is characterized in that the lower part of the first conical flask (4) is positioned in the ice water bath kettle (6), an ice water mixture (7) is filled in the ice water bath kettle (6), a first bottle rubber plug (4-1) is arranged at the bottle opening of the first conical flask (4) and a tar absorbent (5) is filled in the first conical flask (4), the branch pipe (3-1) penetrates through the first bottle rubber plug (4-1) and the pipe opening is positioned below the liquid level of the tar absorbent (5), one end of the first conveying pipe (8) is inserted into the first conical flask (4) from the first bottle rubber plug (4-1), the pipe opening of the first conveying pipe (8) is positioned above the liquid level of the tar absorbent (5), the other end of the first conveying pipe (8) is connected with the inlet of the dryer (9), the outlet of the dryer (9) is connected with one end of the second conveying pipe (10), the other end of the second conveying pipe (10) is connected with the inlet of the mass flowmeter (11), the other end of the second conveying pipe (11) is connected with the third conveying pipe (12), and the other end of the third conveying pipe (12) is connected with the third conveying pipe (12).
9. The method for using the catalyst for pyrolysis and cracking of low-rank coal according to claim 8, wherein: the device is characterized by further comprising an oil moisture measuring device for measuring the moisture quality of the absorbent mixture (5-1) after tar absorption in the first conical flask (4), wherein the oil moisture measuring device comprises a condensation return pipe (15), a moisture measuring pipe (16), a second conical flask (17) and a universal electric furnace (18), the second conical flask (17) is arranged on the universal electric furnace (18) to be heated, the absorbent mixture (5-1) after tar absorption is contained in the second conical flask (17), a second bottle rubber plug (17-1) is arranged on the bottle opening of the second conical flask (17), the condensation return pipe (15) is located above the universal electric furnace (18), the moisture measuring pipe (16) is arranged at the lower end of the condensation return pipe (15), a cold water inlet (15-1) is arranged on one side of the lower portion of the condensation return pipe (15), a cold water outlet (15-2) is arranged on one side of the upper portion of the condensation return pipe (15), and a branch pipe of the moisture measuring pipe (16) is inserted into the liquid surface of the second conical flask (17-1) from the second rubber plug (17-1) to be located on the absorbent mixture (5-absorbent mixture after tar absorption in the conical flask (17).
10. The method for using the catalyst for pyrolysis and cracking of low-rank coal according to claim 9, wherein: the closed end of the quartz tube with the branch pipe (3) horizontally extends into the high-temperature pyrolysis furnace (1), the heating temperature of the universal electric furnace (18) on the second conical bottle (17) is 100-150 ℃, and the heating temperature of the high-temperature pyrolysis furnace (1) on the closed end of the quartz tube with the branch pipe (3) is 450-850 ℃.
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