CN114836240A - Method and system for preparing red mud-biological coke composite catalyst and purifying tar - Google Patents
Method and system for preparing red mud-biological coke composite catalyst and purifying tar Download PDFInfo
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- CN114836240A CN114836240A CN202210535972.5A CN202210535972A CN114836240A CN 114836240 A CN114836240 A CN 114836240A CN 202210535972 A CN202210535972 A CN 202210535972A CN 114836240 A CN114836240 A CN 114836240A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000571 coke Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002309 gasification Methods 0.000 claims abstract description 57
- 239000002028 Biomass Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000428 dust Substances 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000005611 electricity Effects 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 65
- 239000000047 product Substances 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- 238000004523 catalytic cracking Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000002082 metal nanoparticle Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/023—Reducing the tar content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0966—Hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
- C10J2300/1675—Integration of gasification processes with another plant or parts within the plant with the production of electricity making use of a steam turbine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method and a system for preparing a red mud-biological coke composite catalyst and purifying tar, wherein a red mud raw material and a biomass raw material are mixed and dried and then fed into a rotary furnace for carbothermic reduction reaction to obtain the red mud-biological coke composite catalyst, which has a special structure and catalytic activity; and the volatile components generated in the preparation process of the catalyst enter a downdraft type gasification furnace, the volatile components are used as a gasification agent in the gasification furnace to perform pyrolysis gasification reaction with biomass raw materials, the obtained gas product passes through a cyclone dust collector and then enters a fixed bed reformer to perform catalytic reforming reaction under the obtained red mud-biological coke composite catalyst, the content of biomass gasification tar is greatly reduced, and the gas product of the catalytic reforming reaction is driven to a gas turbine through a draught fan and drives a generator to generate electricity. The combustion tail gas is used as a heat source of the rotary furnace and the drum dryer. The whole system has high energy efficiency and low operation cost, and effectively couples the preparation process of the catalyst and the deep purification process of the biomass gasification tar.
Description
Technical Field
The invention belongs to the field of composite catalyst preparation and tar purification, and particularly relates to a method and a system for preparing a red mud-biological coke composite catalyst and purifying tar.
Background
Biomass energy is used as a novel renewable energy source and is increasingly widely applied. The preparation of fuel gas by biomass gasification is an important way for biomass energy utilization, however, tar is inevitably generated in the gasification process, and the existence of tar not only reduces the gasification efficiency, but also can affect the stable operation of the whole gasification system by low-temperature condensation.
The catalytic cracking method is an effective method for removing tar, not only can solve the problem of tar harm, but also can improve the heat value of fuel gas. Therefore, the preparation of the catalyst with low cost and excellent performance becomes the key of the biomass gasification technology. The red mud is industrial waste material produced by a Bayer bauxite process for manufacturing aluminum, and the iron oxide content in the red mud is high, so the red mud has great prospect in the preparation of a catalyst for cracking tar. However, when the red mud is directly used as the tar cracking catalyst, Fe particles are in an oxidation state, the pore structure is poor, the catalytic efficiency is low, sintering and rapid inactivation of metal active sites can be caused after long-term operation in the catalytic process, and the stability of the catalyst is poor, so that the preparation of the composite catalyst by using the biological coke as a catalyst carrier is an effective way to solve the problem. However, the preparation process of the catalyst is usually independent, and besides the solid product is effectively utilized as the catalyst, other products are considered to be harmful byproducts in the preparation process, the treatment is difficult, and the preparation process is independent from the biomass gasification process, and the process coupling problem between the preparation process and the biomass gasification process needs to be solved.
Disclosure of Invention
The invention aims to provide a method and a system for preparing a red mud-biological coke composite catalyst and purifying tar, so as to reduce iron oxide in red mud into a simple substance state and improve the pore structure of the red mud to prepare a high-performance catalyst and use the high-performance catalyst for catalytic cracking of tar to improve the biomass gasification efficiency, and realize effective coupling of the preparation of the catalyst and the biomass gasification process.
The technical solution for realizing the purpose of the invention is as follows:
a method for preparing a red mud-biological coke composite catalyst and purifying tar is used for preparing the red mud-biological coke composite catalyst and for catalytic cracking of the tar to improve the biomass gasification efficiency, and is realized by the following steps:
putting a red mud raw material and a biomass raw material into a mixer for uniform mixing;
the mixed raw materials are sent into a drier for drying until the water content is 5-10 percent;
the dried raw materials enter a rotary furnace to carry out carbon thermal reduction reaction, and the generated solid products are discharged through the rotary furnace to obtain the red mud-biological coke composite catalyst;
transferring the prepared catalyst to a bed layer of a fixed bed reformer after cooling;
volatile matters generated in the preparation process of the catalyst enter a downdraft type gasification furnace through a pipeline, the volatile matters are used as a gasification agent in the gasification furnace to perform pyrolysis gasification reaction together with biomass raw materials, micromolecule oxygen-containing components contained in the gasification agent are used as the gasification agent to promote the gasification reaction process, the generated gas products pass through a cyclone dust collector and enter a fixed bed reformer to perform catalytic reforming reaction, the red mud-biological coke composite catalyst is used for performing deep catalytic cracking on tar in the gas products obtained by the gasification furnace, the tar content in the gas products is reduced, and the purified gas products are driven to a gas turbine through a draught fan and drive a generator to generate electricity;
the combustion tail gas of the gas turbine is used for heating the rotary furnace, then is discharged after heat exchange of the rotary furnace, and is used as a heat source of the drum dryer.
A system for preparing a red mud-biological coke composite catalyst and purifying tar comprises a mixer, a dryer, a rotary furnace, a downdraft gasification furnace, a cyclone dust collector, a fixed bed reformer, an induced draft fan, a gas turbine and a generator;
the outlet of the mixer is connected with the feed inlet of the dryer, the mixer is used for uniformly mixing the red mud raw material and the biomass raw material, and the mixed raw material is fed into the dryer for drying; the dryer is used for drying the mixed raw materials until the water content is 5-10%;
the discharge port of the dryer is connected with the feed port of the rotary furnace, and the rotary furnace is used for carrying out carbothermic reduction reaction on the dried raw materials;
the gas outlet of the rotary furnace is connected with the gas inlet of the downdraft gasifier and is used for carrying out pyrolysis gasification reaction on volatile matters generated by the rotary furnace and biomass raw materials in the gasifier;
the gas outlet of the downdraft gasification furnace is connected with the inlet of the cyclone dust collector, the gas outlet of the cyclone dust collector is connected with the gas inlet of the fixed bed reformer, a gas product enters the fixed bed reformer to perform catalytic reforming reaction, and the red mud-biological coke composite catalyst is used for performing deep catalytic cracking on tar in the gas product obtained by the gasification furnace, so that the tar content in the gas product is reduced;
the gas outlet of the fixed bed reformer is connected with the inlet of an induced draft fan, the outlet of the induced draft fan is connected with the inlet of a gas turbine, and the purified gas product is driven to the gas turbine by the induced draft fan and drives a generator to generate electricity;
the outlet of the gas turbine is connected to the hot flue gas inlet of the rotary furnace and is used for heating the rotary furnace; and the hot flue gas outlet of the rotary furnace is connected with the hot flue gas inlet of the dryer and is used as a heat source of the dryer.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the red mud and biomass are pyrolyzed in situ to prepare the red mud-biological coke composite catalyst, the existence of the biomass promotes the reduction of active metal phase Fe in the red mud from an oxidation state to a Fe simple substance state, and metal nano particles are embedded into a biological coke carrier, the anchoring effect of the metal nano particles can slow down the sintering and agglomeration of the metal particles, the metal nano particles are favorable for maintaining the catalytic activity, the obtained red mud-biological coke composite catalyst presents superior catalytic activity and stability, in addition, the existence of the red mud promotes the catalytic bond breaking of volatile heavy components in the process of pyrolyzing the biomass in situ, and the conversion of the volatile heavy components to micromolecule combustible components is favorable; (2) through the coupling of the system, the preparation process of the catalyst is effectively coupled and associated with the biomass gasification process, volatile components released in the in-situ pyrolysis process of the catalyst enter the upper end of the biomass gasification furnace, and the micromolecule oxygen-containing components are used as gasification agents, so that the quality of biomass gasification products can be effectively improved, and byproducts in the preparation process of the catalyst are also treated; (3) in the aspect of energy utilization, tail gas (with the temperature of 800-; (4) the raw materials adopted by the whole system are only red mud and biomass, the price is low, no pollution is caused, and the cost and complexity of tar removal can be reduced by an efficient strategy.
Drawings
FIG. 1 is a schematic flow structure diagram of a method for preparing a red mud-biological coke composite catalyst and purifying tar;
FIG. 2 shows the effect of different catalysts on tar removal at a catalytic reforming temperature of 700 ℃;
FIG. 3 shows the cycle performance of different catalysts at 700 ℃.
Fig. 4 is SEM and XRD images of the red mud-biocoke composite catalyst.
Detailed Description
The invention is further described with reference to the following figures and embodiments.
With reference to fig. 1, the method for preparing the red mud-biological coke composite catalyst and purifying the tar in this embodiment is used for preparing the red mud-biological coke composite catalyst and for catalytic cracking of the tar to improve the biomass gasification efficiency, and is implemented in the following manner:
the red mud raw material and the biomass raw material are put into a mixer 1 to be uniformly mixed, the mixed raw material is sent into a drum dryer 3, the drying temperature is 150-200 ℃, and the drying is carried out until the water content is 5-10%. The dried raw material enters a rotary furnace 8 to carry out carbon thermal reduction reaction, the pyrolysis temperature is controlled to be 600-800 ℃, and the pyrolysis time is 1-2 hours. The generated solid product is discharged through the rotary kiln 8 so as to obtain the red mud-biological coke composite catalyst, which has special structure and catalytic activity, and mainly shows that Fe-based oxides in the red mud are reduced into Fe simple substances by biomass components in the carbothermic reduction process, the Fe-based oxides are uniformly embedded into a biological coke carrier, the structure of the composite catalyst is enriched, and the prepared catalyst is cooled and then transferred to a bed layer of a fixed bed reformer 21; meanwhile, the mixture of the red mud and the biomass also has the function of catalytic bond breaking on the pyrolysis heavy component in the pyrolysis process, the obtained volatile component is mainly micromolecule combustible component and enters the gas inlet at the upper end of the downdraft type gasification furnace 14 through a pipeline, the gasification agent and the biomass raw material are subjected to pyrolysis gasification reaction in the gasification furnace 14 at the temperature of 600-800 ℃, the reaction time is 0.5-1 hour, the gas product obtained by the gasification furnace 14 is subjected to primary heavy tar and dust removal through the cyclone dust collector 18 and then enters the fixed bed reformer 21 for catalytic reforming reaction, the catalytic reforming reaction mainly aims to utilize the red mud-biological coke composite catalyst to carry out deep catalytic cracking on tar in the gas product obtained by the gasification furnace 14, the temperature of the catalytic reforming reaction is set as 600-700 ℃, and the tar content in the gas product is purified to be lower than the standard of 20-50 mg/cubic meter, driven to the gas turbine 28 by the induced draft fan 25 and drives the generator 31 to generate electricity.
The rotary furnace 8 involved in the carbothermic reduction process prepared by the red mud-biological coke composite catalyst is in an indirect heating type, the heat source of the rotary furnace 8 is derived from combustion tail gas of a gas turbine 28, the temperature range is 800-minus 850 ℃, the heat is exchanged by the rotary furnace 8, the heat is discharged and used as the heat source of the drum dryer 3, the temperature is reduced to 250-minus 350 ℃, and the biomass raw material is discharged after being dried.
Volatile components of the red mud and the biomass in the rotary furnace 8 after the carbothermic reduction reaction enter the upper end gas inlet of the downdraft gasifier 14, and micromolecule oxygen-containing components contained in the volatile components are used as gasifying agents, so that the quality of gas products in the biomass gasification process is further improved, the catalyst preparation process and the biomass gasification process are coupled by the system, and the effective complementation of the two processes is realized.
A system for preparing a red mud-biological coke composite catalyst and purifying tar comprises: a mixer 1, a roller dryer 3, a rotary kiln 8, a downdraft gasifier 14, a cyclone dust collector 18, a fixed bed reformer 21, an induced draft fan 25, a gas turbine 28 and a generator 31;
an outlet 2 of the mixer 1 is connected with a material inlet 4 of a roller dryer 3, a material outlet 5 of the roller dryer 3 is connected with a material inlet 9 of a rotary furnace 8, a pyrolysis volatile component outlet 10 of the rotary furnace 8 is connected with a gas inlet 15 of a downdraft gasifier 14, a gas outlet 17 of the downdraft gasifier 14 is connected with a gas inlet 19 of a cyclone dust collector 18, a gas outlet 20 of the cyclone dust collector 18 is connected with a gas inlet 22 of a fixed bed reformer 21, a gas outlet 24 of the fixed bed reformer 21 is connected with an inlet 26 of an induced draft fan 25, a gas outlet 27 of the induced draft fan 25 is connected with a gas inlet 29 of a gas turbine 28, and a hot flue gas outlet 30 of the gas turbine 28 is connected with a hot flue gas inlet 13 of the rotary furnace 8 to supply heat for the rotary furnace 8.
A hot flue gas outlet 11 of the rotary furnace 8 is connected to a hot flue gas inlet 6 of the drum dryer 3, and hot flue gas is discharged through a hot flue gas outlet 7 after releasing heat in the drum dryer 3. The solid product outlet 12 of the rotary kiln 8 is connected to the bed 23 of the fixed bed reformer 21.
Examples
Uniformly mixing and stirring red mud and sawdust according to a ratio of 1:1, drying at 105 ℃ for 24 hours, performing carbon thermal reduction (in-situ pyrolysis) in nitrogen inert atmosphere for 1 hour to obtain the red mud-biological coke composite catalystA coke catalyst; the characterization structure shows that the crystalline phase structure of the red mud-biological coke composite catalyst mainly presents Fe 0 The surface area of the red mud-biological coke composite catalyst obtained by the method of the invention reaches 99.56m 2 The specific surface area of the red mud/biological coke catalyst obtained by directly mixing and pyrolyzing the pyrolytic coke and the red mud is 53.16m 2 The result of the invention shows that the catalyst has obviously improved pore structure. In addition, the results of the three catalysts of Red Mud (RM), red mud/biocoke (RM/C) and red mud-biocoke (RM/SD) on the purification and removal of tar at the catalytic reforming temperature of 700 ℃ are shown in fig. 2. The result shows that the catalytic removal rate of the red mud-biological coke composite catalyst on tar is the highest and reaches 88.77 percent due to the developed pore structure and the dispersed metal activity phase points; fig. 3 is a cycle performance test of three different catalysts at 700 ℃, and the test shows that the red mud-biocoke composite catalyst obtained by the invention has the highest stability, and the tar removal rate is reduced after 9 cycles, because the sintering of metal nanoparticles is slowed down by the interaction of the carbon carrier and the metal nanoparticles, and the oxidation of the metal Fe nanoparticles is reduced by the carbon carrier as a medium of a reduction reaction. The surface morphology of the composite catalyst can be seen from the SEM image in fig. 4, and it can be observed that a large number of nanoparticle clusters with irregular morphology and non-uniform particle size distribution exist in the catalyst, which shows the characteristic that the metal nanoparticles are embedded in the porous carbon carrier. The anchoring effect of the carbon carrier on the metal nano-particles can slow down the sintering and agglomeration of the metal particles, and is beneficial to the maintenance of the catalytic activity of the metal nano-particles. The XRD image shows that most of Fe substance of the composite catalyst is further reduced and exists in the form of simple substance. During carbothermic reduction, reducing gases (H) from the volatiles formed by wood chip decomposition 2 And CO) making most of the Fe 2 O 3 Is reduced to Fe 0 The tar removal capacity of the catalyst is enhanced. The red mud-biological coke composite catalyst obtained by the method is a novel catalyst for deep purification of tar.
Claims (6)
1. A method for preparing a red mud-biological coke composite catalyst and purifying tar is used for preparing the red mud-biological coke composite catalyst and for catalytic cracking of the tar to improve the biomass gasification efficiency, and is characterized by being realized by the following steps:
putting a red mud raw material and a biomass raw material into a mixer for uniform mixing;
the mixed raw materials are sent into a drier for drying until the water content is 5-10 percent;
the dried raw materials enter a rotary furnace to carry out in-situ carbothermic reduction reaction, and the generated solid products are discharged through the rotary furnace to obtain the red mud-biological coke composite catalyst;
transferring the prepared catalyst to a bed layer of a fixed bed reformer after cooling;
volatile matters generated in the preparation process of the catalyst enter a downdraft type gasification furnace through a pipeline, the volatile matters are used as a gasification agent in the gasification furnace to perform pyrolysis gasification reaction together with biomass raw materials, micromolecule oxygen-containing components contained in the gasification agent are used as the gasification agent to promote the gasification reaction process, the generated gas products pass through a cyclone dust collector and enter a fixed bed reformer to perform catalytic reforming reaction, the red mud-biological coke composite catalyst is used for performing deep catalytic cracking on tar in the gas products obtained by the gasification furnace, the tar content in the gas products is reduced, and the purified gas products are driven to a gas turbine through a draught fan and drive a generator to generate electricity;
the combustion tail gas of the gas turbine is used for heating the rotary furnace, then is discharged after heat exchange of the rotary furnace, and is used as a heat source of the dryer.
2. The method for preparing the red mud-biological coke composite catalyst and purifying the tar according to claim 1, wherein the temperature for the carbothermic reduction reaction in the rotary furnace is 600-800 ℃ and the time is 1-2 hours.
3. The method for preparing the red mud-biological coke composite catalyst and purifying the tar according to claim 1, wherein the temperature of the pyrolysis gasification reaction in the gasification furnace is 600-800 ℃, and the reaction time is 0.5-1 hour.
4. The method for preparing the red mud-biological coke composite catalyst and purifying the tar as claimed in claim 1, wherein the temperature of the catalytic reforming reaction of the fixed bed reformer is 600-700 ℃, and the tar content in the purified gas product is purified to be lower than 20-50 mg/cubic meter.
5. A system for preparing a red mud-biological coke composite catalyst and purifying tar is characterized by comprising a mixer, a dryer, a rotary furnace, a downdraft gasification furnace, a cyclone dust collector, a fixed bed reformer, an induced draft fan, a gas turbine and a generator;
the outlet of the mixer is connected with the feed inlet of the dryer, the mixer is used for uniformly mixing the red mud raw material and the biomass raw material, and the mixed raw material is fed into the dryer for drying; the dryer is used for drying the mixed raw materials until the water content is 5-10%;
the discharge port of the dryer is connected with the feed port of the rotary furnace, and the rotary furnace is used for carrying out carbothermic reduction reaction on the dried raw materials;
the gas outlet of the rotary furnace is connected with the gas inlet of the downdraft gasifier and is used for carrying out pyrolysis gasification reaction on volatile matters generated by the rotary furnace and biomass raw materials in the gasifier;
the gas outlet of the downdraft gasification furnace is connected with the inlet of the cyclone dust collector, the gas outlet of the cyclone dust collector is connected with the gas inlet of the fixed bed reformer, a gas product enters the fixed bed reformer to perform catalytic reforming reaction, and the red mud-biological coke composite catalyst is used for performing deep catalytic cracking on tar in the gas product obtained by the gasification furnace, so that the tar content in the gas product is reduced;
the gas outlet of the fixed bed reformer is connected with the inlet of an induced draft fan, the outlet of the induced draft fan is connected with the inlet of a gas turbine, and the purified gas product is driven to the gas turbine by the induced draft fan and drives a generator to generate electricity;
the outlet of the gas turbine is connected to the hot flue gas inlet of the rotary furnace and is used for heating the rotary furnace; and the hot flue gas outlet of the rotary furnace is connected with the hot flue gas inlet of the dryer and is used as a heat source of the dryer.
6. The system for preparing the red mud-biological coke composite catalyst and purifying the tar according to claim 5, wherein the system couples a catalyst preparation process and a biomass gasification tar deep purification process.
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| CN101225315A (en) * | 2007-12-18 | 2008-07-23 | 中国科学院广州能源研究所 | Method and device for biomass compound gasification |
| CN106010657A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院广州能源研究所 | Low-tar gasification method for biomass and device for implementing method |
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| CN101225315A (en) * | 2007-12-18 | 2008-07-23 | 中国科学院广州能源研究所 | Method and device for biomass compound gasification |
| CN106010657A (en) * | 2016-05-18 | 2016-10-12 | 中国科学院广州能源研究所 | Low-tar gasification method for biomass and device for implementing method |
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