CN105273764B - Coal gasification apparatus and gasification process - Google Patents
Coal gasification apparatus and gasification process Download PDFInfo
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- CN105273764B CN105273764B CN201410355461.0A CN201410355461A CN105273764B CN 105273764 B CN105273764 B CN 105273764B CN 201410355461 A CN201410355461 A CN 201410355461A CN 105273764 B CN105273764 B CN 105273764B
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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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- 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
- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to a kind of loading catalyst Coal Under gasification installation and gasification process, solve the problems, such as that the technological parameters such as coal gasification temperature in the prior art is high, carbon conversion ratio is low result in and high energy consumption high to equipment requirement.The present invention carries out gasification reaction with gasifying agent under the effect of the catalyst by using coal, mainly including fluidized-bed reactor (12), cyclone separator (13), heat-exchange apparatus (14), cleaning equipment (15);Fluidized-bed reactor (12), which is provided with, radially has feed inlet I (27), feed inlet II (28), bottom is provided with air inlet (24), and fluidized-bed reactor (12) is divided into lower part emulsion zone (26) and top dilute-phase zone (29);Cyclone separator (13) includes " J " type pipe blanking section (34) and " J " type pipe discharging section (35), the present invention passes through intermittent deslagging, realize the coal dust low temperature gasification in reactor apparatus, reduce the production cost of synthesis gas and the requirement to equipment, recycle catalyst, charcoal percent conversion is improved, this technical solution preferably solves the problems, such as this, available in coal gasification industrial production.
Description
Technical field
The present invention relates to a kind of loading catalyst Coal Under gasification installation and gasification process.
Background technology
China is the country of deficency rich in coal and poor in oil, with the increasingly reduction of oil and natural gas resource, is developed clean efficient
Coal conversion technology have far-reaching significance.
Traditional Coal Gasification Technology, i.e. coal are at high temperature with the gasifying agent that oxygen or air and vapor form into promoting the circulation of qi
Change, generation synthesis gas (mainly hydrogen, carbon monoxide and carbon dioxide) can be substantially divided into three categories:High pressure fixed bed gas
Change, entrained flow gasification and fluidized gasification etc..The Coal Gasification Technology has that the temperature needed for gasification reaction is high, and energy consumption is big, pair sets
It is standby to require the shortcomings of high.
Loading catalyst Coal Under gasification installation and gasification process are a kind of important ways that coal cleaning efficiently utilizes, and are adopted
With catalytic coal gasifaction technology, gasifying agent of the coal at relatively low temperature with vapor, air or oxygen composition is being catalyzed
Gasification reaction is carried out under the action of agent, generates synthesis gas, which has gasification temperature compared with other Coal Gasification Technologies
Low, synthesis Gas content is high, the advantages such as low to equipment Requirement condition.
The technology can be such that the material being fluidized is sufficiently mixed with catalyst, be conducive to heat transfer, mass transfer and gasification reaction, favorably
In the utilization of granular material, but the deficiencies of the loss that also brings carbon in ash in discharge and cyclone separator simultaneously is larger.
USP4,057,402 proposes a kind of fluidized gasification process, and coal is by pre-processing laggard fluidized bed reactor
In, lime-ash is excluded using ash agglomerating method, flying dust is first detached through stove internal cyclone separators, then is detached through stove external cyclone separator, is followed
The carbon containing flying dust of ring returns to gasification installation from molten poly- separating pipe, and the gasification will first pass through stove internal cyclone under the condition of high temperature
Separator, so requiring its material higher, flying dust is recycled by the molten separator for gathering ash, and operation and control is difficult.
US4,077,778 proposes using multistage fluidized bed coal catalytic gasification technique, eliminates the deficiency of former catalysis gasification technique,
Make the progress that gasification is more efficient, make full use of charging carbon resource, improve efficiency of carbon con version.Main fluidized-bed operating gas velocity is higher, by portion
Point carbon particle is carried secretly to two level fluid bed, compared with gasification reaction is carried out under low gas velocity, is increased the residence time of solid particle, maximum
Limit improves efficiency of carbon con version.Multistage fluidized bed coal catalytic gasification technique uses multiple fluidized-bed reactors, and equipment investment is huge, behaviour
Make more complicated.
GPE companies of the U.S. make further research on the basis of EXXON technologies, and US20070000177AI is disclosed
The technique of coal one-step method methane, catalyst are alkali metal oxide or alkali metal salt, and gasifying agent is vapor, main skill
Art feature is also added into calcium oxide to the coal dust of reaction, absorbing reaction other than adding in efficient methanation catalyst
The carbon dioxide that process generates further improves methane content, and the determining of above-mentioned technique is the catalysis generated due to adding in methane
Agent, but high temperature does not utilize the generation of methane, and for reaction temperature general control at 700 DEG C or so, reaction speed is slow, needs to be additionally provided
Heat maintains reaction temperature, these technologies are also still in development phase.
Invention content
The problem of the first technical problem to be solved by the present invention is in the prior art high to coal gasification temperature, carries
A kind of new coal gasification apparatus is gone out.The device can be used for coal gasification production, has the mild gasification for realizing coal, fluidizes simultaneously
The advantages of bed apparatus design is simple, and then low for equipment requirements.
The second technical problem to be solved by the present invention is that the problem of efficiency of carbon con version is low exists in the prior art, and use is above-mentioned
A kind of coal gasification apparatus, it is proposed that new coal gasification method.This method can be used for coal gasification production, have temperature low, carbon turns
The advantages of rate is high, while low to process energy consumption consumption.
One of to solve above-mentioned technical problem, the technical solution adopted in the present invention is as follows:A kind of loading catalyst condition
Lower coal gasification apparatus, capital equipment include crushing plant 7, milling apparatus 8, equipment 9, drying equipment 10, fluid bed are mixed
Reactor 12, cyclone separator 13, heat-exchange apparatus 14, cleaning equipment 15, wherein 10 top of fluidized-bed reactor are dilute-phase zone
29 and lower part be emulsion zone 26, lower part emulsion zone 26 is provided with radially fed mouth I 27 and feed inlet II 28, and bottom is equipped with air-distribution device
25 and air inlet 24;Top dilute-phase zone 29 is provided with gas vent 30 and is connected to cyclone separator 13, has in cyclone separator 13 point
From room 31, complete gas solid separation, " J " type pipe blanking section 34 and " J " type pipe discharging section 35 arranged at lower part, Cyclone outlet 33 and
Heat-exchange apparatus 14 is connected;Gas after heat exchange after gas purifying equipment 16 by collecting.
In above-mentioned technical proposal, the loading catalyst Coal Under gasification installation, it is characterized in that coal and catalyst exist
It is completed in milling apparatus, the milling apparatus is ball mill or colloidal mill.The top of the fluidized-bed reactor 12 is dilute
The diameter ratio of phase region 29 and lower part emulsion zone 26 is (2.0~10.5):1;The ratio between height is (3.0~12.0):1.Described
The radially fed mouth I 27 of lower part emulsion zone and feed inlet II 28 are axially symmetric disposition and horizontal sextant angle is 45 DEG C.The whirlwind point
" J " type pipe blanking section (34) bottom from device is provided with ash discharging hole (36), and " J " type pipe discharging section (34) is apart from bottom ash discharging hole (36)
For 30~60cm.
Loading catalyst Coal Under gasification installation is proposed in the present invention, it is therefore intended that better mixed coal powder and catalysis
Agent, the unreacted pulverized coal particle of high efficiente callback effectively reduce gasification temperature and improve charcoal percent conversion, while simple using design
Fluidized-bed reactor, and then the technique is made to be suitble to the coal gasification methods of low cost and extensive processing China's rich reserves.
To solve above-mentioned technical problem two, the technical solution used in the present invention is as follows:Coal dust and catalyst by grinding,
Dipping, stirring, are uniformly mixed, mixed coal dust and catalyst enter as raw material in fluidized-bed reactor, are connect with gasifying agent
It touches, 0.1~3MPa is calculated as with gauge pressure in reaction pressure, the mean temperature of conversion zone is 650~800 DEG C, air velocity 0.1
Under conditions of~0.6m/s, catalyst coal dust surface erosion, trepanning, reduce reaction activity, convert coal into synthesis gas, ash
Product, the higher synthesis gas of temperature passes through heat exchange recovery section heat.
In above-mentioned technical proposal, the catalyst can be basic anhydride, metal salt, and wherein basic anhydride can be
Fe2O3、CaO、MgO、K2O and Na2At least one of O etc.;Metal salt can be KCl, K2CO3、K2SO4And Na2CO3In
It is at least one.It is 20~200 μm that the coal dust and catalyst, which is milled to granularity, and the weight ratio of catalyst and coal is (0.05
~0.20):1.The emulsion zone flow velocity is 0.4~0.6m/s, and dilute-phase zone flow velocity is 0.1~0.4m/s.
Coal dust and catalyst are milled to 20~200 μm of designated size in the method for the present invention, in equipment is mixed fully
Mixing, makes catalyst granules effectively be attached on pulverized coal particle, effectively expands the contact area of coal dust, allows pulverized coal particle rear
Phase further expands the surface area of micropore when gasifying, catalyst forms complex compound with coal, reduces chemical energy, so as to change reaction
Dynamic conditions improves reaction efficiency, and by the coal dust of attached catalyst, air or oxygen and vapor are added under reactor
The emulsion zone in portion, emulsion zone are in mild gasification reaction state, and flow velocity is 0.4~0.6m/s, and as reaction carries out, catalyst is attached
On semicoke enter top dilute-phase zone, the region have better gas-solid contact area and higher reaction temperature, more added with
Conducive to the gasification of semicoke, the flow velocity of top dilute-phase zone is more advantageous to reacting, and flow velocity is 0.1~0.4m/s, and temperature is 650~800
DEG C, the particle (containing unreacted carbon and catalyst etc.) of cyclone separator is entered through the discharging of " J " type pipe by top dilute-phase zone
Section returns to reactor lower part emulsion zone and participates in reaction, also catalyst is enable to recycle while carbon conversion ratio is improved.
Additionally due to the method for the present invention, temperature of reactor is greatly lowered, and realizes the mild gasification of coal, and reducing will to equipment
It asks and the processing to cooling gas, makes operation more convenient, effectively raise the utilization of energy, reduce heat loss, drop
The low energy consumption of technique.
The process unit and method of the present invention is described above, but those skilled in the art obviously can be according to the present invention
Content a series of variations are carried out to the present invention.Although the present invention, which focuses on, illustrates that coal prepares synthesis gas, it is apparent that the side of the present invention
Method can also be used to processing petroleum coke or biomass, while can also be used to prepare coal tar etc..Various change to what the present invention was done
Dynamic or modification, such equivalent forms equally fall within patent requirements appended by the application and limit range.
Method using the present invention realizes the mild gasification of coal, reduces the requirement to equipment for gasification and reduces coal
The consumption of energy in gasification.Fluidized-bed reactor dilute-phase zone is 10.5 with fluidized-bed reactor emulsion zone diameter ratio:1,
The ratio between height is 12.0:1, the mean temperature of fluidized-bed reactor is 800 DEG C, and coal average particle size is 100um, and catalyst is averaged grain
It spends for 100um, on this condition, after gasification in gas composition, CO2, CO, H2And CH4The 2.8% of gas composition is accounted for,
56.1%, 25.2% and 13.2%, charcoal percent conversion reaches 95%.
Description of the drawings
Fig. 1 is a kind of loading catalyst Coal Under gasification installation structure diagram.
In Fig. 1,1 is coal;2 be catalyst;3 be carrier gas;4 be air (oxygen);5 be vapor;6 be carrier gas;7 be broken
Equipment;8 be milling apparatus;9 is are mixed equipment;10 be drier;11 be feeding system;12 be fluidized-bed reactor;13
For cyclone separator;14 be heat exchanger;15 be clarifier;16 be fluid reservoir;17 be preheater;18 be ash discharge cinder notch;19 be coal
Gas;20 be heat recovery.
Fig. 2 is the apparatus structure detailed annotation figure of feeding system, fluidized-bed reactor and cyclone separator.In Fig. 2, (a) is Fig. 1
In feeding system 11 detailed annotation figure, (b) is detailed annotation figure of the fluidized-bed reactor 12 in Fig. 1, and (c) is the whirlwind point in Fig. 1
Detailed annotation figure from device 13, wherein 21 be coal bunker;22 be screw feeder;23 export for batcher lower end;24 be air inlet;25 are
Air-distribution device;26 be reactor emulsion zone;27 be " J " type pipe returning charge entrance;28 be furnace charge entrance;29 be reactor dilute-phase zone;
30 be syngas outlet;31 be cyclone separator separation chamber;32 be cyclone inlet;33 be Cyclone outlet;34
For " J " type pipe blanking section;35 be " J " type pipe discharging section;36 be ash discharging hole.
Feed coal 1 is broken by crushing plant 7, and crushing plant 7 is connected with milling apparatus 8, is ground, 2 (alkali of catalyst
Property oxide or alkali metal) into being ground in milling apparatus 8;Milling apparatus 8 is connected with equipment 9 is mixed, mixed
It closes and is impregnated, stirred in mixing plant 9, uniformly mixed coal and catalyst are added into feeding system after drier 10 is dried
Coal bunker 21 in 11, coal bunker 21 are connected to screw(-type) feeder 22, coal and catalyst below and are conveyed by screw(-type) feeder 22, by feed
Machine lower end outlet 23 is sent to being reacted in reactor emulsion zone 26;The synthesis gas and ash of generation divide by cyclone separator 13
From rear, ash enters " J " type pipe blanking section 34, and using " J " type pipe discharging section 35, " J " type pipe discharging section 35 is returned with emulsion zone
Material entrance 28 is connected, and last ash is back to reactor emulsion zone 26 and is fully gasified again;Circulating fluid bed reactor produces
Raw clinker is discharged from reactor bottom 24, and the gas separated enters heat-exchange apparatus 14, heat-exchange apparatus 14 with it is net
Change device equipment 15 to be connected.
Below by embodiment, the present invention is further elaborated, but is not limited to originally apply example.
Specific embodiment
【Embodiment 1】
In the technological reaction flow path device shown in Fig. 1,2, fluidized-bed reactor dilute-phase zone and the close phase of fluidized-bed reactor
Area's diameter ratio is 4.0:1, the ratio between height is 3.0:1, coal in crushing plant through preliminary is crushed, is ground in milling apparatus
Average particle size is 100um, and catalyst is ground to average particle size as 100um in milling apparatus, the average temperature of fluidized-bed reactor
It is 700 DEG C to spend, and fluidized-bed reactor top pressure is calculated as 0.1MPa with gauge pressure, and the radially fed mouth of fluidized-bed reactor is by feed
System control inlet amount, axial admission mouth is to measure the amount of pump-metered vapor;Linear gas velocity is in fluidized-bed reactor emulsion zone
0.4m/s, fluidized-bed reactor dilute-phase zone linear gas velocity are 0.1m/s.Catalyst is Na2CO3, the amount of catalyst and the weight of coal
Than being 0.05:1, the fluctuation of bed mean temperature is kept within ± 30 DEG C, after gasification in gas composition, CO2, CO, H2And CH4
Account for about the 2%, 57%, 28% and 10% of gas composition, remaining is unreacted O2With inert gas etc., charcoal percent conversion reaches
To 85%.
【Embodiment 2】
According to condition described in embodiment 1, the average particle size of coal is 100um, and the average particle size of catalyst is 100um, is flowed
Fluidized bed reactor dilute-phase zone is 6.5 with fluidized-bed reactor emulsion zone diameter ratio:1, the ratio between height is 7.0:1, fluid bed is anti-
The mean temperature for answering device is 750 DEG C, and fluidized-bed reactor top pressure is calculated as 2.5MPa, catalyst Fe with gauge pressure2O3, catalysis
The amount of agent and the weight ratio of coal are 0.10:1, the fluctuation of bed mean temperature is kept within ± 30 DEG C, gas composition after gasification
In, CO2, CO, H2And CH4Account for about the 3%, 55%, 25% and 12% of gas composition, remaining is unreacted O2And indifferent gas
Body etc., charcoal percent conversion reaches 90%.
【Embodiment 3】
According to condition described in embodiment 1, the average particle size of coal is 100um, and the average particle size of catalyst is 100um, is flowed
Fluidized bed reactor dilute-phase zone is 10.5 with fluidized-bed reactor emulsion zone diameter ratio:1, the ratio between height is 12.0:1, fluid bed
The mean temperature of reactor is 800 DEG C, and fluidized-bed reactor top pressure is calculated as 3.0MPa, catalyst K with gauge pressure2CO3, urge
The amount of agent and the weight ratio of coal are 0.15:1, the fluctuation of bed mean temperature is kept to keep fluidized-bed reaction within ± 30 DEG C
Device trouble-free operation, after gasification in gas composition, CO2, CO, H2And CH4Account for about the 2.8% of gas composition, 56.1%,
25.2% and 13.2%, remaining is unreacted O2With inert gas etc., charcoal percent conversion reaches 95%.
【Comparative example 1】
Conventional atmospheric Winkler Coal Gasification Technologies gasification temperature is in 950 DEG C or more, after gasification in gas composition, CO2,
CO, H2And CH4Account for about the 17%, 25%, 32% and 0.8% of gas composition, remaining is unreacted O2With inert gas etc.,
Charcoal percent conversion is only 81%.
【Comparative example 2】
Conventional high-tension Winkler Coal Gasification Technologies gasification temperature is in 1000 DEG C or more, after gasification in gas composition, CO2,
CO, H2And CH4Account for about the 8.2%, 48.2%, 30.6% and 2.8% of gas composition, remaining is unreacted O2And indifferent gas
Body etc., charcoal percent conversion is 91%.
Claims (7)
1. a kind of loading catalyst Coal Under gasification that loading catalyst Coal Under gasification process, wherein the method use
Device, capital equipment include crushing plant (7), milling apparatus (8), equipment (9), drying equipment (10), fluid bed are mixed
In reactor (12), cyclone separator (13), heat-exchange apparatus (14), cleaning equipment (15), wherein fluidized-bed reactor (12),
Top is dilute-phase zone (29), lower part is emulsion zone (26), and lower part emulsion zone (26) is provided with radially fed mouth I (27), feed inlet II
(28), bottom is equipped with air-distribution device (25) and air inlet (24);Top dilute-phase zone (29) is provided with gas vent (30) and is connected to rotation
Wind separator (13), cyclone separator (13) Nei You separation chambers (31) complete gas solid separation, and cyclone separator (13) lower part has
" J " type pipe blanking section (34) and " J " type pipe discharging section (35), Cyclone outlet (33) are connected with heat-exchange apparatus (14);
Gas after heat exchange is collected afterwards by gas purifying equipment (16);
Wherein, the diameter ratio of the fluidized-bed reactor (12) top dilute-phase zone (29) and lower part emulsion zone (26) is (2.0
~10.5):1;The ratio between height is (3.0~12.0):1;
Coal gasification method under the conditions of above-mentioned loading catalyst is:Coal dust and catalyst mix equal by grinding, dipping, stirring
Even, mixed coal dust and catalyst enter as raw material in fluidized-bed reactor, are contacted with gasifying agent, in reaction pressure with table
Pressure is calculated as 0.1~3MPa, and the mean temperature of conversion zone is 650~800 DEG C, and catalyst is in coal dust surface erosion, trepanning, reduction
Reaction activity, converts coal into the product of synthesis gas and ash, and the higher synthesis gas of temperature passes through heat exchange recovery section heat;
Wherein, the emulsion zone flow velocity in the coal gasification apparatus is 0.4~0.6m/s, and dilute-phase zone flow velocity is 0.1~0.4m/s.
2. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that coal and catalyst are being ground
It is ground in equipment, the milling apparatus is ball mill or colloidal mill.
3. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that fluidized-bed reactor (12)
Bottom is equipped with air-distribution device (25), and hole is triangle, hexagon or circle.
4. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that the lower part emulsion zone
(26) radially at least there are two feed inlet, feed inlet I (27) and feed inlet II (28), and it is axially symmetric disposition and horizontal sextant angle
It is 45 DEG C.
5. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that " J " type of cyclone separator
Pipe blanking section (34) bottom is provided with ash discharging hole (36), and " J " type pipe discharging section (34) is 30~60cm apart from bottom ash discharging hole (36).
6. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that catalyst is alkaline oxygenated
Object or metal salt, wherein basic anhydride are Fe2O3、CaO、MgO、K2O and Na2At least one of O;Metal salt for KCl,
K2CO3、K2SO4And Na2CO3At least one of.
7. loading catalyst Coal Under gasification process according to claim 1, it is characterized in that coal dust and catalyst are ground
It is 20~200 μm to be milled to granularity, and the weight ratio of catalyst and coal is (0.05~0.20):1.
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CN108018088A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of catalytic coal gasifaction |
CN108342222A (en) * | 2017-01-24 | 2018-07-31 | 杨秋良 | Application process of the vanadium based gas catalyst on coal-fired industry fluid bed or air flow bed |
CN108179032A (en) * | 2018-01-09 | 2018-06-19 | 新奥科技发展有限公司 | A kind of fluidized-bed gasification furnace, gasification system and method |
CN108410506B (en) * | 2018-04-13 | 2020-04-21 | 新奥科技发展有限公司 | Anaerobic catalytic gasification furnace, catalytic gasification system and coal methanation method |
CN111057585B (en) * | 2018-10-17 | 2021-08-03 | 中国石油化工股份有限公司 | Method for fluidized coal gasification |
CN110373230A (en) * | 2019-07-29 | 2019-10-25 | 安徽工业大学 | A kind of method that fluidized gasification flying dust returns furnace gas |
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CN1221777A (en) * | 1997-12-31 | 1999-07-07 | 中国科学院广州能源研究所 | Method and appts. for producing medium-heat value combustible gas from oxygen gasified of biological substances |
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