CN108018088A - A kind of method of catalytic coal gasifaction - Google Patents
A kind of method of catalytic coal gasifaction Download PDFInfo
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- CN108018088A CN108018088A CN201610964256.3A CN201610964256A CN108018088A CN 108018088 A CN108018088 A CN 108018088A CN 201610964256 A CN201610964256 A CN 201610964256A CN 108018088 A CN108018088 A CN 108018088A
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- gas
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- bed reactor
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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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
- C10J3/56—Apparatus; Plants
-
- 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
- C10J2300/093—Coal
-
- 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
- C10J2300/0973—Water
-
- 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
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention belongs to catalytic coal gasifaction technical field, and the present invention provides a kind of method of catalytic coal gasifaction.This method includes realizing intermittent charging by controlling the pressure difference of fluidized-bed reactor to control, adjusted by temperature programming to temperature of reactor, sample pyrolysis is complete in constant temperature to bed, water flowing steam or hydrogen start to react, gas after reaction is through cyclone separator, gas-liquid separator, drier, product gas volume is measured by wet flow indicator, product gas composition passes through Agilent on-line chromatographic analysis, the conversion ratio that coal gasification is converted into gas-phase product reaches 95%, and the accumulation growing amount of methane reaches 11.4mmolg‑1.The technology can the intermittent charging of realization device, reduce experiment in tear stove and shove charge number open, optimize technique, reduces the cost, improve catalytic gasification efficiency.
Description
Technical field
Patent of the present invention is related to a kind of method of catalytic coal gasifaction.
Background technology
With being continuously increased for coal in China output and consumption figure, the high-efficiency cleaning of coal using becoming pendulum in China
Important topic in face of researcher.Coal Gasification Technology is one of key technology that following coal high-efficiency cleaning utilizes, and is China's energy
The strategy of sustainable development in source provides important leverage.Core technology and guiding technology as cleaning coal utilization technology, coal
Catalytic gasification technology causes the advantages of Coal Clean is efficiently utilized, shorten technological process, improve industrial economy
The close attention of domestic and international researcher.
But Coal Gasification Technology is hindered further due to the problems such as high water consume, high energy consumption, high cost and fluctuation of service
Promotion and application.This inhibition has also directly facilitated the research and development of catalytic coal gasifaction technology, endangers from last century oil
During machine, the gasification of coal low temperature catalyst was once just the research hotspot of coal chemical industry scholar.The gasification of coal catalyst is the solid states in coal
Lower progress, catalyst uniformly mixes according to a certain percentage with pulverized coal particle, and the catalyst of coal surface distribution leads to
The effect of erosion fluting is crossed, coal is preferably contacted with gasifying agent and accelerates gasification reaction.Core as cleaning coal utilization technology
Technology and guiding technology, catalytic coal gasifaction technology have Coal Clean is efficiently utilized, shorten technological process, improve industry gives birth to
The advantages that economy of production, so as to cause the close attention of domestic and international researcher.
The research of catalyst occupies critical positions in catalytic coal gasifaction technology.Catalytic coal gasifaction often selects alkali metal, alkali
The hydroxide and carbonate of earth metal and transition-metal catalyst etc., wherein alkali metal are that the highest monomer of generally acknowledged efficiency is urged
Agent, cheap and efficient catalyst is the research hotspot of catalytic coal gasifaction in recent years.
Catalytic coal gasifaction technology is currently under the research and extension stage, at present in the field technology research comparative maturity
There are Exxon mobil companies and GPE companies.The Exxon mobil companies in the U.S. are developed with alkali metal in the 1970s
Or alkaline-earth metal salt and hydroxide such as K2CO3And Na2CO3-Ca(OH)2For the catalysis Coal Gasification Technology of catalyst.GPE is in recent years
To develop the one-step method natural gas from coal technology for combining the workshop sections such as traditional gasification, purification, methanation（" blue gas
Technology "）.Domestic many research structures be also dedicated to natural gas from coal in terms of research, such as：Chinese Academy of Sciences's Shanxi coal chemistry
Research institute, Xinao Technology Development Co., Ltd, Zhejiang University, East China University of Science etc..Current research also in experimental stage,
There is not industrialized report.The Coal Gasification Technology direct gasification, shortens coal gasification reaction path, still, the direct synthesizing methane of coal
Efficiency have much room for improvement.According to the change of experimental condition during experiment, stove and shove charge number, and experimental rig are repeatedly torn open
It is small, it is difficult to realize continuous feed.
The content of the invention
Goal of the invention：Patent of the present invention provides a kind of method of catalytic coal gasifaction, can the intermittent charging of realization device, subtract
Few coal dust entrainment, increase coal gas contact, optimize technique, reduces in experiment and tears stove and shove charge number open, reduce the cost, and improves coal catalysis
Gasification efficiency.
Technical solution：
Unstripped gas preheats after water inlet device, vaporizer with entering preheater after being mixed by the carrier gas of mass flowmenter, from stream
Change bed bottom enters fluidized-bed reactor, coal dust and catalyst and enters fluidized-bed reactor, unstripped gas and coal from coal dust feeding gas
Powder reacts in fluidized-bed reactor produces reaction gas, and reaction gas passes through cyclone separator, into gas-liquid separator, drier,
Finally obtain product gas.
Usually, the technique is suitable for laboratory's coal high temperature catalytic gasification reaction, preferably 600 DEG C -900 of reaction temperature
DEG C, react coal-water ratio preferably 2 g/ (g/min) -10g/ (g/min), reaction pressure preferably 2 MPa -3.5MPa.
The unstripped gas uses axial admission, and unstripped gas is one or both of water vapour, hydrogen.
The catalyst is the organic salt of alkali or alkaline earth metal.
The fluidized-bed reactor, including air inlet, distribution grid, reactor inner cylinder, air inlet, gas outlet, metal baffle；
The air inlet is located at the lower end of reactor inner cylinder, and gas outlet is located at the upper end of reactor inner cylinder, and metal baffle is located at fluid bed
The port of export of reactor；Fluidized-bed reactor is upper coarse and lower fine.
The fluidized-bed reactor, it is characterised in that have insulating layer and heat block, reactor inner cylinder outside reactor inner cylinder
Bottom is equipped with slag-drip opening, and slag-drip opening is connected with distribution grid.
The fluidized-bed reactor, it is characterised in that fluidized-bed reactor top particle size and the diameter ratio of lower part thin footpath are
2:1, highly than 1:4.
Invention effect：
（1）Unstripped gas has declined before entering fluidized-bed reactor lower end by mass flowmenter pressure, can be with fluidized-bed reaction
Device upper end produces 0.3MPa-0.5MPa micro-positive pressures, enables fluidized-bed reactor intermittent feeding.
（2）Fluidized-bed reactor is upper coarse and lower fine, and the diameter ratio of particle size and thin footpath is 2:1, highly than 1:4.Increase coal dust with
Reaction gas time of contact, catalytic coal gasifaction efficiency is improved, the port of export is equipped with a small amount of catalyst coal that metal baffle will be carried secretly wherein
Powder separates.
（3）Catalytic coal gasifaction effect is optimal, and the conversion ratio that coal gasification is converted into gas-phase product reaches 95%, the accumulation of methane
Growing amount reaches 11.4mmolg-1。
Brief description of the drawings
Intermittent fluidized bed processes figure in Fig. 1 embodiment of the present invention.
Fig. 2 is fluidized-bed reactor structure diagram in embodiment.
In figure, depressurized before 01- water inlet devices, 02- vaporizers, 03- preheaters, 04- fluidized-bed reactors, 05-
Valve, 06- mass flowmenters, 07- coal dusts feeder, 08- condensers, 09- gas-liquid separators, 10- driers, 11- counterbalance valves,
12- wet flow indicators, 13- slag-drip openings, 14- air inlets, 15- insulating layers, 16- distribution grids, 17- heat blocks, in 18- reactors
Cylinder, 19- gas outlets, 20- metal baffles.
Embodiment
Below by way of embodiments and drawings, the method for the present invention is described in detail, but embodiment is merely to illustrate hair
It is bright and be not meant to limit the scope of the invention.
Embodiment 1
Fluidized-bed reactor, including air inlet 14, distribution grid 16, reactor inner cylinder 18, air inlet 14, gas outlet 19, metal gear
Plate 20；Air inlet 14 is located at the lower end of reactor inner cylinder 18, and gas outlet 19 is located at the upper end of reactor inner cylinder 18, metal baffle 20
Positioned at the port of export of fluidized-bed reactor 4；Fluidized-bed reactor 4 is upper coarse and lower fine, and top particle size and the diameter ratio of lower part thin footpath are
2:1, highly than 1:4.There are insulating layer 15 and heat block 17 outside reactor inner cylinder 18, reactor inner cylinder bottom is equipped with slag-drip opening 13,
Slag-drip opening 13 is connected with distribution grid 16.
Raw material air water is after water inlet device, vaporizer with entering preheater after being mixed by the carrier gas nitrogen of mass flowmenter
Preheating, enters fluidized-bed reactor, coal dust and catalyst YK from fluidized-bed bottom and enters fluidized-bed reactor from coal dust feeding gas,
Coal dust is reacted with water in fluidized-bed reactor produces reaction gas, and coal-water ratio is：5 g/ (g/min), reaction pressure is：
3.0MPa, reaction temperature：700 DEG C, the micro-positive pressure of fluidized-bed reactor upper end is：0.5MPa, reaction gas pass through cyclone separator,
Into gas-liquid separator, drier, finally obtains product gas（Methane）.Product gas enters after wet flow indicator metered volume
Aglient7890A chromatographics form.Methane production（Accumulate growing amount）Definition is：YCH4 = nCH4/ Mcoal,
The gas-phase product conversion ratio that coal is changed into：The result shows that
Coal gasification is converted into gas-phase product.270min is reacted, the conversion ratio that coal gasification is converted into gas-phase product reaches 95%, methane
Accumulation growing amount reaches 11.4mmolg-1[m1] 。
Embodiment 2
Fluidized-bed reactor, including air inlet 14, distribution grid 16, reactor inner cylinder 18, air inlet 14, gas outlet 19, metal gear
Plate 20；Air inlet 14 is located at the lower end of reactor inner cylinder 18, and gas outlet 19 is located at the upper end of reactor inner cylinder 18, metal baffle 20
Positioned at the port of export of fluidized-bed reactor 4；Fluidized-bed reactor 4 is upper coarse and lower fine, and top particle size and the diameter ratio of lower part thin footpath are
2:1, highly than 1:4.There are insulating layer 15 and heat block 17 outside reactor inner cylinder 18, reactor inner cylinder bottom is equipped with slag-drip opening 13,
Slag-drip opening 13 is connected with distribution grid 16.
Raw material air water is after water inlet device, vaporizer with entering preheater after being mixed by the carrier gas nitrogen of mass flowmenter
Preheating, enters fluidized-bed reactor, coal dust and catalyst YK-K from fluidized-bed bottom2CO3It is anti-from coal dust feeding gas into fluidized bed
Device is answered, coal dust is reacted with water in fluidized-bed reactor produces reaction gas, and coal-water ratio is：7 g/g/min, reaction pressure is：
2.5.0MPa, reaction temperature：900 DEG C, the micro-positive pressure of fluidized-bed reactor upper end is：0.4MPa, reaction gas pass through cyclonic separation
Device, into gas-liquid separator, drier, finally obtains product gas（Methane）.Product gas after wet flow indicator metered volume, into
Enter Aglient7890A chromatographics composition.Methane production（Accumulate growing amount）Definition is：YCH4 = nCH4/
Mcoal, the gas-phase product conversion ratio that coal is changed into：Knot
Fruit shows that gas-phase product conversion ratio reaches 88%, and the accumulation growing amount of methane is 9.7mmolg-1。
Embodiment 3
Fluidized-bed reactor, including air inlet 14, distribution grid 16, reactor inner cylinder 18, air inlet 14, gas outlet 19, metal gear
Plate 20；Air inlet 14 is located at the lower end of reactor inner cylinder 18, and gas outlet 19 is located at the upper end of reactor inner cylinder 18, metal baffle 20
Positioned at the port of export of fluidized-bed reactor 4；Fluidized-bed reactor 4 is upper coarse and lower fine, and top particle size and the diameter ratio of lower part thin footpath are
2:1, highly than 1:4.There are insulating layer 15 and heat block 17 outside reactor inner cylinder 18, reactor inner cylinder bottom is equipped with slag-drip opening 13,
Slag-drip opening 13 is connected with distribution grid 16.
Raw material air water is after water inlet device, vaporizer with entering preheater after being mixed by the carrier gas nitrogen of mass flowmenter
Preheating, enters fluidized-bed reactor, coal dust and catalyst YK-KOH are anti-from coal dust feeding gas into fluidized bed from fluidized-bed bottom
Device is answered, coal dust is reacted with water in fluidized-bed reactor produces reaction gas, and coal-water ratio is：10 g/g/min, reaction pressure is：
3.5Mpa, reaction temperature：600 DEG C, the micro-positive pressure of fluidized-bed reactor upper end is：0.3MPa, reaction gas pass through cyclone separator,
Into gas-liquid separator, drier, finally obtains product gas（Methane）.Product gas enters after wet flow indicator metered volume
Aglient7890A chromatographics form.Methane production（Accumulate growing amount）Definition is：YCH4 = nCH4/ Mcoal,
The gas-phase product conversion ratio that coal is changed into：The result shows that
Pressure increase, gas-phase product conversion ratio reduces, and is conducive to the generation of methanation reaction, in 3.5Mpa, reacts 270min, gas phase
Product yield reaches 85%, and the accumulation growing amount of methane is 9.0mmolg-1。
Embodiment 4
Fluidized-bed reactor, including air inlet 14, distribution grid 16, reactor inner cylinder 18, air inlet 14, gas outlet 19, metal gear
Plate 20；Air inlet 14 is located at the lower end of reactor inner cylinder 18, and gas outlet 19 is located at the upper end of reactor inner cylinder 18, metal baffle 20
Positioned at the port of export of fluidized-bed reactor 4；Fluidized-bed reactor 4 is upper coarse and lower fine, and top particle size and the diameter ratio of lower part thin footpath are
2:1, highly than 1:4.There are insulating layer 15 and heat block 17 outside reactor inner cylinder 18, reactor inner cylinder bottom is equipped with slag-drip opening 13,
Slag-drip opening 13 is connected with distribution grid 16.
Raw material air water is after water inlet device, vaporizer with entering preheater after being mixed by the carrier gas nitrogen of mass flowmenter
Preheating, enters fluidized-bed reactor, coal dust and catalyst YK-KOH are anti-from coal dust feeding gas into fluidized bed from fluidized-bed bottom
Device is answered, coal dust is reacted with water in fluidized-bed reactor produces reaction gas, and coal-water ratio is：2 g/g/min, reaction pressure is：
3.5Mpa, reaction temperature：800 DEG C, the micro-positive pressure of fluidized-bed reactor upper end is：0.3MPa, reaction gas pass through cyclone separator,
Into gas-liquid separator, drier, finally obtains product gas（Methane）.Product gas enters after wet flow indicator metered volume
Aglient7890A chromatographics form.Methane production（Accumulate growing amount）Definition is：YCH4 = nCH4/ Mcoal,
The gas-phase product conversion ratio that coal is changed into：The result shows that
Pressure increase, gas-phase product conversion ratio reduces, and is conducive to the generation of methanation reaction, in 2.0Mpa, reacts 270min, gas phase
Product yield reaches 82%, and the accumulation growing amount of methane is 8.7mmolg-1。
In conclusion in experimentation, conversion experiment condition can directly be fed, small-sized batch fluidized bed device reaction device
Multiple condition test does not have to tear stove open in test of many times, directly purges deslagging, reduces cost of labor.
Claims (8)
- A kind of 1. method of catalytic coal gasifaction, it is characterised in that unstripped gas is after water inlet device, vaporizer with passing through mass flowmenter Carrier gas mixing after enter preheater preheat, from fluidized-bed bottom enter fluidized-bed reactor, coal dust and catalyst from coal dust into Material gas enters fluidized-bed reactor, and unstripped gas is reacted with coal dust in fluidized-bed reactor produces reaction gas, and reaction gas is through overwinding Wind separator, into gas-liquid separator, drier, finally obtains product gas.
- 2. method according to claim 1, it is characterised in that unstripped gas into fluidized-bed reactor be axial admission, unstripped gas It is one or both of water vapour, hydrogen.
- 3. method according to claim 1, it is characterised in that unstripped gas is water, 2-10 g/ (g/min) of coal-water ratio.
- 4. method according to claim 1, it is characterised in that reaction pressure is 2 MPa -3.5Mpa, reaction temperature 600 ℃-900℃。
- 5. method according to claim 1, it is characterised in that catalyst uses the organic salt of alkali or alkaline earth metal.
- 6. the fluidized-bed reactor in method according to claim 1, it is characterised in that：Including air inlet, distribution grid, reaction Device inner cylinder, air inlet, gas outlet, metal baffle；The air inlet is located at the lower end of reactor inner cylinder, and gas outlet is located at reactor The upper end of inner cylinder, metal baffle are located at the port of export of fluidized-bed reactor；Fluidized-bed reactor is upper coarse and lower fine.
- 7. fluidized-bed reactor according to claim 6, it is characterised in that there are insulating layer and heat block outside reactor inner cylinder, Reactor inner cylinder bottom is equipped with slag-drip opening, and slag-drip opening is connected with distribution grid.
- 8. fluidized-bed reactor according to claim 6, it is characterised in that fluidized-bed reactor top particle size and lower part are thin The diameter ratio in footpath is 2:1, highly than 1:4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774549A (en) * | 2018-08-29 | 2018-11-09 | 中国石油化工股份有限公司 | Air flow bed fine coal hydrogasification stove, hydrogasification system and hydro-gasification process |
| CN110938474A (en) * | 2019-12-17 | 2020-03-31 | 新奥科技发展有限公司 | Method for loading papermaking black liquor on coal sample, fluidized bed furnace and system |
| CN115216347A (en) * | 2022-06-24 | 2022-10-21 | 沈阳航空航天大学 | Fluidized bed gasification and fixed bed methanation coupling system and method |
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| CN115216347A (en) * | 2022-06-24 | 2022-10-21 | 沈阳航空航天大学 | Fluidized bed gasification and fixed bed methanation coupling system and method |
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Application publication date: 20180511 |