CN114836240B - 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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- CN114836240B CN114836240B CN202210535972.5A CN202210535972A CN114836240B CN 114836240 B CN114836240 B CN 114836240B CN 202210535972 A CN202210535972 A CN 202210535972A CN 114836240 B CN114836240 B CN 114836240B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000000571 coke Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002028 Biomass Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000002309 gasification Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 15
- 239000000428 dust Substances 0.000 claims abstract description 13
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- 230000005611 electricity Effects 0.000 claims abstract description 5
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 67
- 239000000047 product Substances 0.000 claims description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 238000004523 catalytic cracking Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000002156 mixing 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
- 239000000779 smoke Substances 0.000 claims description 4
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 description 14
- 239000002082 metal nanoparticle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000011946 reduction process Methods 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
- 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
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 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
- 239000000969 carrier Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- 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, which are characterized in that 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, wherein the red mud-biological coke composite catalyst has a special structure and catalytic activity; volatile matters generated in the preparation process of the catalyst enter a downdraft gasifier, the volatile matters are used as gasifying agents in the gasifier to carry out pyrolysis gasification reaction with biomass raw materials, the obtained gas products enter a fixed bed reformer to carry out catalytic reforming reaction under the condition of the obtained red mud-bio-coke composite catalyst after passing through a cyclone dust collector, the content of tar in biomass gasification is greatly reduced, and the gas products of the catalytic reforming reaction are driven to a gas turbine by an induced draft fan and drive 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 running cost, and effectively couples the preparation process of the catalyst and the deep purification process of biomass gasification tar.
Description
Technical Field
The invention belongs to the field of composite catalyst preparation and tar purification, and in particular 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 utilizing biomass energy, however, tar is inevitably generated in the gasification process, the presence of tar not only reduces gasification efficiency, but also can affect the stable operation of the whole gasification system by condensation at low temperature.
The catalytic cracking method is an effective method for removing tar, not only can solve the problem of harm of tar, but also can improve the heat value of fuel gas. Therefore, the preparation of the catalyst with low cost and excellent performance becomes a key of biomass gasification technology. The red mud is an industrial waste material generated by the Bayer bauxite process for manufacturing aluminum, and the content of ferric oxide in the red mud is high, so that the red mud has a great prospect in the preparation of a tar cracking catalyst. However, when red mud is directly used as a tar cracking catalyst, fe particles are in an oxidation state, the pore structure is poor, the catalytic efficiency is low, and sintering and rapid deactivation of metal active sites can be caused by long-term operation in the catalytic process, so that the catalyst stability is poor, and the preparation of a composite catalyst by taking biological coke as a catalyst carrier is an effective way to solve the problem. However, in general, the process of preparing the catalyst is independent, and in the preparation process, besides the solid product being the catalyst, other products are considered as harmful byproducts, the treatment is difficult, and the process is independent of the biomass gasification process, so that the problem of process coupling between the two is 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, which are used for reducing ferric oxide in red mud into an elemental state and improving the pore structure of the ferric oxide to prepare a high-performance catalyst and for catalytic cracking of the tar so as to improve the biomass gasification efficiency and realize the 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:
the preparation method of the red mud-biological coke composite catalyst and the tar purification method are used for preparing the red mud-biological coke composite catalyst and for tar catalytic cracking to improve the biomass gasification efficiency, and are realized by the following steps:
putting the red mud raw material and the biomass raw material into a mixer for uniform mixing;
the mixed raw materials are sent into a dryer for drying until the water content is 5 to 10 percent;
the dried raw materials enter a rotary furnace to carry out carbothermic reduction reaction, and the generated solid products are discharged through the rotary furnace to obtain the red mud-biological coke composite catalyst;
the prepared catalyst is transferred to a bed layer of a fixed bed reformer after being cooled;
volatile matters generated in the catalyst preparation process enter a downdraft gasifier through a pipeline, pyrolysis gasification reaction is carried out in the gasifier together with biomass raw materials as a gasifying agent, micromolecular oxygen-containing components contained in the gasifying agent are used as the gasifying agent to promote the gasification reaction process, the generated gas products enter a fixed bed reformer to carry out catalytic reforming reaction through a cyclone dust collector, tar in the gas products obtained in the gasifier is subjected to deep catalytic pyrolysis by utilizing a red mud-bio-coke composite catalyst, 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 tail gas generated by combustion of the gas turbine is heated by the rotary furnace, is discharged after heat exchange by 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 gasifier, 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, and the mixer is used for uniformly mixing the red mud raw material and the biomass raw material, and the mixed raw material is sent 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 gasifier 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, the gas product enters the fixed bed reformer to carry out catalytic reforming reaction, and the red mud-biological coke composite catalyst is used for carrying out deep catalytic cracking on tar in the gas product obtained by the gasifier, 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 purified gas products are driven to the gas turbine by the induced draft fan and drive a generator to generate electricity;
the gas turbine outlet is connected to a hot flue gas inlet of the rotary furnace and is used for heating the rotary furnace; and the hot smoke outlet of the rotary furnace is connected with the hot smoke inlet of the dryer and is used as a heat source of the dryer.
Compared with the prior art, the invention has the remarkable advantages that:
(1) The red mud-biological coke composite catalyst is prepared by in-situ pyrolysis of red mud and biomass, the existence of the biomass promotes the reduction of active metal phase Fe in the red mud from an oxidation state to an Fe simple substance state, metal nano particles are embedded into a biological coke carrier, the anchoring effect of the metal nano particles on the metal nano particles can slow down sintering and agglomeration of the metal particles, the metal nano particles can keep catalytic activity, the obtained red mud-biological coke composite catalyst shows excellent catalytic activity and stability, and in addition, the existence of the red mud promotes the catalytic bond breaking of volatile heavy components in the in-situ pyrolysis process of the biomass, and is favorable for conversion of the volatile components into micromolecular combustible components; (2) Through the coupling of the system, the preparation process of the catalyst is effectively coupled with the biomass gasification process, volatile matters released in the in-situ pyrolysis process of the catalyst enter the upper end of the biomass gasification furnace, and the oxygen-containing components of small molecules are utilized 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 800-850 ℃) generated by burning a biomass gasification product through a gas turbine is used as a heat source of a catalyst in-situ pyrolysis rotary furnace, the reaction temperature is 600-800 ℃, the temperature difference is suitable, the biomass gasification product is discharged after heat exchange through the rotary furnace and then used as a heat source of a drum dryer, the temperature is reduced to 250-350 ℃, the biomass raw material is dried and then discharged, and the whole system process can realize self-supply of energy; (4) The raw materials adopted by the whole system are only red mud and biomass, so that the cost is low, pollution is avoided, and meanwhile, the cost and complexity of tar removal can be reduced by an efficient strategy.
Drawings
FIG. 1 is a schematic flow chart of a preparation and tar purification method of a red mud-bio-coke composite catalyst;
FIG. 2 shows the purification and removal effects of different catalysts on tar at a catalytic reforming temperature of 700 ℃;
FIG. 3 is a graph showing the cycle performance test of different catalysts at 700 ℃.
Fig. 4 is an SEM, XRD image of the red mud-bio-coke composite catalyst.
Detailed Description
The invention is further described with reference to the drawings and specific embodiments.
Referring to fig. 1, the method for preparing the red mud-bio-coke composite catalyst and purifying tar in the embodiment is used for preparing the red mud-bio-coke composite catalyst and for catalytic cracking of tar to improve the biomass gasification efficiency, and is realized by the following steps:
the red mud raw material and the biomass raw material are placed in a mixer 1 to be evenly mixed, the mixed raw material is sent into a drum dryer 3, the drying temperature is 150-200 ℃, and the raw material is dried until the water content is 5-10%. The dried raw materials enter a rotary furnace 8 for carbothermic reduction reaction, the pyrolysis temperature is controlled to be 600-800 ℃, and the pyrolysis time is controlled to be 1-2 hours. The produced solid product is discharged through a rotary furnace 8 to obtain a red mud-biological coke composite catalyst which has a special structure and catalytic activity, and is mainly characterized in that Fe-based oxides in the red mud are reduced into Fe simple substances by biomass components in the carbothermic reduction process, and are uniformly embedded into biological coke carriers, the structure of the composite catalyst is enriched, and the prepared catalyst is transferred to a bed layer of a fixed bed reformer 21 after being cooled; meanwhile, the red mud and biomass mixture has the effect of catalyzing and breaking bonds of pyrolyzed heavy components, the obtained volatile components mainly comprise micromolecular combustible components, enter the upper end gas inlet of the downdraft gasifier 14 through a pipeline, are subjected to pyrolysis gasification reaction together with biomass raw materials in the gasifier 14 as gasifying agents at 600-800 ℃ for 0.5-1 hour, and after the heavy tar and dust are primarily removed from gas products obtained by the gasifier 14 through the cyclone dust collector 18, enter the fixed bed reformer 21 for catalytic reforming reaction, the main purpose is to utilize the red mud-biological coke composite catalyst to carry out deep catalytic pyrolysis on tar in the gas products obtained by the gasifier 14, the catalytic reforming reaction temperature is set to 600-700 ℃, and after the tar content in the gas products is purified to be lower than 20-50 mg/cubic meter standard, the gas products are driven to the gas turbine 28 through the induced draft fan 25 and the generator 31 for power generation.
The rotary furnace 8 involved in the carbothermic reduction process for preparing the red mud-biological coke composite catalyst is of an indirect heating type, a heat source is derived from combustion tail gas of the gas turbine 28, the temperature range is 800-850 ℃, the heat is exchanged by the rotary furnace 8 and then discharged to be used as a heat source of the drum dryer 3, the temperature is reduced to 250-350 ℃, and the biomass raw material is dried and then discharged.
Volatile components of red mud and biomass in the rotary kiln 8 after carbothermic reduction reaction enter into a gas inlet at the upper end of the downdraft gasifier 14, and micromolecular 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 effective complementation of the two processes is realized.
A system for preparing a red mud-biological coke composite catalyst and purifying tar comprises: mixer 1, drum dryer 3, rotary kiln 8, downdraft gasifier 14, cyclone dust collector 18, fixed bed reformer 21, induced draft fan 25, gas turbine 28, generator 31;
the outlet 2 of the mixer 1 is connected with the material inlet 4 of the drum dryer 3, the material outlet 5 of the drum dryer 3 is connected with the material inlet 9 of the rotary furnace 8, the pyrolysis volatile outlet 10 of the rotary furnace 8 is connected with the gas inlet 15 of the downdraft gasifier 14, the gas outlet 17 of the downdraft gasifier 14 is connected with the gas inlet 19 of the cyclone 18, the gas outlet 20 of the cyclone 18 is connected with the gas inlet 22 of the fixed bed reformer 21, the gas outlet 24 of the fixed bed reformer 21 is connected with the inlet 26 of the induced draft fan 25, the gas outlet 27 of the induced draft fan 25 is connected with the gas inlet 29 of the gas turbine 28, and the hot flue gas outlet 30 of the gas turbine 28 is connected to the hot flue gas inlet 13 of the rotary furnace 8 to supply heat to the rotary furnace 8.
The hot flue gas outlet 11 of the rotary kiln 8 is connected to the hot flue gas inlet 6 of the drum dryer 3, and the hot flue gas is discharged through the hot flue gas outlet 7 after being released 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
The red mud and the wood dust are uniformly mixed and stirred according to the proportion of 1:1, dried for 24 hours at 105 ℃, and subjected to carbothermic reduction (in-situ pyrolysis) for 1 hour under nitrogen inert atmosphere to obtain the red mud-biological coke composite catalyst; characterization structure finds that Fe is mainly presented in the crystal phase structure of the red mud-biological coke composite catalyst 0 The surface area of the simple substance phase red mud-biological coke composite catalyst obtained by adopting the method of the invention reaches 99.56m 2 Per gram, 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 And/g, showing that the catalyst obtained by the invention significantly improves the pore structure of the catalyst. In addition, the purification and removal effects of three catalysts of Red Mud (RM), red mud/bio-coke (RM/C) and red mud-bio-coke (RM/SD) on tar at the catalytic reforming temperature of 700 ℃ are shown in the result of FIG. 2. As a result, the red mud-biological coke composite catalyst obtained by the invention has the highest catalytic removal rate of tar reaching 88.77 percent due to the developed pore structure and dispersed metal active phase points; FIG. 3 shows the cycle performance test of three different catalysts at 700 ℃, and the test shows that the red mud-bio-coke composite catalyst obtained by the invention has the highest stability, and the tar removal rate is reduced to a lower degree after 9 cycles, because of the mutual interaction of the carbon carrier and the metal nano-particlesThe sintering of the metal nano particles is slowed down by the action, and the carbon carrier is used as a medium of the reduction reaction, so that the oxidation of the metal Fe nano particles is reduced. The SEM image of fig. 4 shows the surface morphology of the composite catalyst, and it can be observed that a large number of nanoparticle clusters with irregular morphology and uneven particle size distribution exist in the catalyst, and the characteristic that the metal nanoparticles are embedded into the porous carbon carrier is presented. 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 metal nano-particles to maintain the catalytic activity. It can be seen from the XRD pattern that the majority of the Fe species of the composite catalyst are further reduced and exist as simple substances. In the carbothermic reduction process, reducing gas (H) in volatile matters generated by decomposition of wood chips 2 And CO) such that a majority of Fe 2 O 3 Is reduced to Fe 0 The tar removing 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 (3)
1. The preparation method of the red mud-biological coke composite catalyst and the tar purification method are used for preparing the red mud-biological coke composite catalyst and for tar catalytic cracking to improve the biomass gasification efficiency, and are characterized by comprising the following steps of:
putting the red mud raw material and the biomass raw material into a mixer for uniform mixing;
the mixed raw materials are sent into a dryer for drying until the water content is 5% -10%;
the dried raw materials enter a rotary furnace to carry out an in-situ carbothermic reduction reaction, and the generated solid products are discharged through the rotary furnace to obtain a red mud-biological coke composite catalyst;
the prepared catalyst is transferred to a bed layer of a fixed bed reformer after being cooled;
volatile matters generated in the catalyst preparation process enter a downdraft gasifier through a pipeline, pyrolysis gasification reaction is carried out in the gasifier together with biomass raw materials as a gasifying agent, micromolecular oxygen-containing components contained in the gasifying agent are used as the gasifying agent to promote the gasification reaction process, the generated gas products enter a fixed bed reformer to carry out catalytic reforming reaction through a cyclone dust collector, tar in the gas products obtained in the gasifier is subjected to deep catalytic pyrolysis by utilizing a red mud-bio-coke composite catalyst, 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 tail gas generated by combustion of the gas turbine is heated by the rotary furnace, is discharged after heat exchange by the rotary furnace, and is used as a heat source of the dryer;
the temperature of the carbothermic reaction in the rotary furnace is 600-800 ℃ and the time is 1-2 hours;
the temperature of pyrolysis gasification reaction in the gasification furnace is 600-800 ℃, and the reaction time is 0.5-1 hour;
the temperature of the catalytic reforming reaction carried out by 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.
2. The system for preparing the red mud-biological coke composite catalyst and purifying the tar is characterized by comprising a mixer, a dryer, a rotary furnace, a downdraft gasifier, 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, and the mixer is used for uniformly mixing the red mud raw material and the biomass raw material, and the mixed raw material is sent 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 gasifier 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, the gas product enters the fixed bed reformer to carry out catalytic reforming reaction, and the red mud-biological coke composite catalyst is used for carrying out deep catalytic cracking on tar in the gas product obtained by the gasifier, 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 purified gas products are driven to the gas turbine by the induced draft fan and drive a generator to generate electricity;
the gas turbine outlet is connected to a hot flue gas inlet of the rotary furnace and is used for heating the rotary furnace; and the hot smoke outlet of the rotary furnace is connected with the hot smoke inlet of the dryer and is used as a heat source of the dryer.
3. The system for preparing the red mud-bio-coke composite catalyst and purifying the tar according to claim 2, wherein the system is coupled with a preparation process of the catalyst 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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