CN103131443A - New technology for preparing clean fuel by coking coal tailings - Google Patents
New technology for preparing clean fuel by coking coal tailings Download PDFInfo
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- CN103131443A CN103131443A CN2011103742847A CN201110374284A CN103131443A CN 103131443 A CN103131443 A CN 103131443A CN 2011103742847 A CN2011103742847 A CN 2011103742847A CN 201110374284 A CN201110374284 A CN 201110374284A CN 103131443 A CN103131443 A CN 103131443A
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- oil
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- 239000003245 coal Substances 0.000 title claims abstract description 100
- 238000004939 coking Methods 0.000 title claims abstract description 20
- 239000000446 fuel Substances 0.000 title claims abstract description 11
- 238000005516 engineering process Methods 0.000 title claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000005188 flotation Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- 239000012265 solid product Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 16
- 239000007764 o/w emulsion Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 230000004064 dysfunction Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241000772415 Neovison vison Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000005439 thermosphere Substances 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007233 catalytic pyrolysis Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 11
- 239000010866 blackwater Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011449 brick Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
New technology for preparing clean fuel by coking coal tailings is characterized in that coking coal tailings (coal slime) are conveyed into a feeding device with a gas locking function through a conveying device, then are conveyed into an externally-heated pyrolytic device for coal catalytic pyrolysis. The pyrolytic device comprises three layers; the external layer is a thermal insulation layer; the intermediate layer is a pyrolysis reaction chamber; and the internal layer is a combustion chamber. The catalyst is added into the tailings (coal slime) in proportion through an adder disposed on a conveyer belt. The pyrolytic gas obtained after condensation and separation of pyrolytic products enters the combustion chamber for combustion. The pyrolytic liquid obtained by condensation and separation is subjected to pyrolytic oil recovery through oil-water separation, and is rectified to obtain light components and heavy components. The light components are processed to prepare oil for flotation; the heavy components are emulsified to prepare emulsified oil, and also enter the combustion chamber for combustion. The solid products formed by pyrolysis are discharged into a coke quenching device from a discharge port at the bottom to recover pyrolytic coke. Coking coal catalytic pyrolysis is performed; the process is simple, convenient for realization, and has good application prospects.
Description
Affiliated technical field
The present invention relates to a kind of coking coal tail coal and prepare the clean fuel new technology, purpose is that the tail coal (coal slime) to coking coal carries out catalyse pyrolysis, and preparation pyrolysis Jiao, pyrolysis gas and pyrolysis liquid carry out the efficient utilization of tail coal (coal slime).The invention belongs to Coal Chemical Industry, coal processing and utilization and field of environment protection.
Background technology
Tail coal is that the black water that produces in the coal separation process passes through the higher waste of ash content that dehydrates formation, and productive rate generally accounts for 5%～8% of feed coal, estimates about 6000～8,000 ten thousand tons of the annual coking coal tail coal that produces of China.Because ash content and the moisture of tail coal are higher, ash content is generally even higher more than 30%, and moisture is up to more than 25%, thereby thermal value is lower, has limited its effectively processing and utilization.The coal situation is nervous, when condition of sales is better, tail coal can mix in commercial coal in a large number and sell, perhaps the fuel as coal gangue power plant is used for combustion power generation together with middle coal, coal gangue, the part tail coal also for the production of moulded coal or directly bake bricks, the mud of heating up water, calcined lime, some tail coal also mixes to be made the coal slime slurry and burns or gasify in black water.But; when the coal sales situation eases up; many tail coals will be stored up even and throw aside; particularly be in remote districts or do not build the colliery of coal gangue power plant; tail coal usually can be stored up even in a large number and throw aside; not only cause loss and the waste of precious resources, and can cause that ecological environmental pollution even destroys.Obviously, carry out the research of tail coal efficient technique of rainwater utilization, not only can effectively utilize waste resource, save high-quality coal, and can eliminate tail coal and store up and even throw aside the environmental pollution that causes, protection is ecological, beautify environment of mining area.
In view of this, the contriver has carried out the research of tail coal efficient technique of rainwater utilization, adopts catalyse pyrolysis technique, utilizes coking coal tail coal (coal slime), has made well behaved pyrolysis Jiao, pyrolysis gas and pyrolysis oil.
Summary of the invention
The present invention proposes and utilize coking coal tail coal (coal slime) catalyse pyrolysis, preparation pyrolysis Jiao, pyrolysis gas and pyrolysis oil are to carry out the high efficient energy sources utilization of tail coal (coal slime).
(1) technological process
Coking coal tail coal (coal slime) catalyse pyrolysis of indication of the present invention, technique unit comprise raw materials pretreatment and delivery system, raw material mixing system, pyrolytic reaction system, condensation and oil and gas separating system, coke discharging and quench system, Controlling System etc.
In pyrolytic process, tail coal (coal slime) to the material mixer with lock airway dysfunction, mixes and the processing that homogenizes at this by tape transport through fragmentation and pre-treatment, then enters in external-heat pyrolysis reaction unit and carries out catalyse pyrolysis.
The pyrolytic reaction device mainly is comprised of three-decker, and internal layer is the combustion chamber, and the centre is the pyrolytic reaction chamber, is formed by different refractory material layings respectively.Skin is insulating, is built by laying bricks or stones by heat insulation and lagging material to form, and outermost layer is reinforced by carbon steel.
Double fuel heat supply, the oil in water emulsion that the pyrolysis gas that forms in the combustion and pyrolysis process respectively and the emulsification of heavy pyrolysis oil make are adopted in the combustion chamber.The outer wall that the flue gas that the combustion chamber generates is directly sent into the pyrolytic reaction chamber circulates, and keeping reaction chamber temperature even, and promotes pyrolytic reaction.Pyrolysis temperature is controlled at 820 ℃～950 ℃, pyrolysis time and is controlled at 60min-300min.In order to guarantee abundant pyrolysis, and improve the productive rate of pyrolysis product, adopt the mode of segmentation pyrolysis to carry out catalyse pyrolysis.Low temperature pyrogenation stage wherein, when temperature was between room temperature to 350 ℃, temperature rise rate was controlled at 5 ℃ of-30 ℃/min and is advisable.In the warm solution stage, temperature is between 380 ℃～800 ℃, temperature rise rate is controlled at 20 ℃ of-100 ℃/min and is advisable.In the high temperature pyrolysis stage, temperature is between 800 ℃～950 ℃, and temperature rise rate is controlled between 10 ℃ of-50 ℃/min and is advisable.
Catalyzer used in pyrolytic process is to be added by the adder that is arranged on conveying belt, and addition is controlled to be 0.5%～5% of raw material add-on.Test-results shows, can be used for the catalyzer that tail coal (coal slime) catalyse pyrolysis uses can be basic metal, alkaline-earth metal, transition metal oxide and composition thereof, can be also coal gangue, slag, lime-ash and industrial residue etc.Wherein be suitable for the main chemical constitution of the materials such as coal gangue, slag, lime-ash and industrial residue that tail coal (coal slime) catalyse pyrolysis uses with Al
2O
31%～10%, SiO
21%～10%, Fe
2O35%～60%, CaO5%～95%, MgO5%～90%, Na
2O1%～10%, K
2O1%～10% is advisable.
The volatile matter that forms in pyrolytic process enters condenser system, through condensation separation, obtains pyrolysis gas and pyrolysis liquid.Directly enter combustion chambers burn after the pyrolysis gas metering, for pyrolytic process provides heat.Get simultaneously gas and carry out compositional analysis.
Pyrolysis liquid obtains pyrolysis oil and water through after oily water separation.Pyrolysis oil rectifying between 105 ℃～360 ℃ obtains light component and heavy component.Light component is used for the floatation process of coal separating plant through processing the preparation flotation oil.Heavy component obtains oil in water emulsion through Over emulsfication, enters combustion chambers burn, is similarly pyrolytic process heat is provided.Meanwhile, utilize respectively liquid chromatograph to carry out the compositional analysis of oil product.The water of separating, through entering condenser system after purifying treatment, the heat-eliminating medium of using as condensation separation.
The solid product that forms in pyrolytic process enters coke quencher through the discharge port discharge of bottom, pyrolytic reaction chamber, forms pyrolysis after quenching burnt, discharges of the coke by the spiral device that discharges of the coke.Pyrolysis Jiao has sloughed volatile matter and a certain amount of sulphur content in Coking Process, thereby sulphur content is relatively low and when burning is smokeless, in addition in pyrolytic process due to the coking effect, form the coke button with certain lumpiness and intensity, so can be used as smokeless fuel, carry out civilian even industrial application.Pyrolysis Jiao can measure by technical analysis, ultimate analysis, thermal value and combustionproperty and carry out property representation.
Embodiment
In recent years, the contriver has successively carried out the catalyse pyrolysis experimental study of ground tail coals (black water) such as opening Luan, Fenxi, has successfully made well behaved pyrolysis burnt.These tests prepare pyrolysis Jiao for coking coal tail coal (coal slime) catalyse pyrolysis, and successful enforcement example is provided.
Open Luan black water catalyse pyrolysis test
Select out black water (the sample 1:M of two the settling tank lower floors of coal separating plant in Luan
ad45.13%, A
ad19.63%; Sample 2:M
ad42.14%, A
ad25.13%), add industrial residue (Al
2O
33.09%, SiO
22.05%, Fe
2O
35.43%, CaO47.06%, MgO38.43%, K
2O1.55%, Na
2O2.39%) carried out catalyse pyrolysis, the output that draws pyrolysis gas is respectively 183.78m
3And 154.33m
3, the productive rate of pyrolysis oil is respectively 10.36% and 7.45%.Further the pyrolysis oil of sample 1 has been carried out rectifying under 205 ℃, the productive rate that draws light component and heavy component is respectively 29.64% and 70.36%.Pyrolysis Jiao's productive rate is respectively 52.09% and 56.12%, further pyrolysis Jiao has been carried out technical analysis, and result is as shown in table 1.As seen, the ash content of pyrolysis Jiao's ash content and black water is closely related.
Table 1 is opened Luan black water pyrolysis Jiao's technical analysis
| Sample | The pyrolysis coke yield | M ad | A ad | V ad | FC ad |
| Sample 1 | 52.09％ | 0.27 | 25.34 | 3.29 | 71.10 |
| Sample 2 | 56.12％ | 0.44 | 49.53 | 1.71 | 48.33 |
(1) Fenxi tail coal catalyse pyrolysis test
The filter cake of choosing Fenxi two coal separating plants of Mining Group company has carried out the catalyse pyrolysis test, and technical analysis and the results of elemental analyses of sample are shown in Table 2.Catalyzer adopts mine tailings, and chemical constitution is: SiO
22.71%, Al
2O
34.35%, Fe
2O
361.95%, CaO5.92%, MgO5.67%, TiO
27.83%, V
2O
59.79%.Pyrolysis Jiao, pyrolysis gas and pyrolysis liquid have been made by catalyse pyrolysis.Wherein pyrolysis gas output is respectively 145.78m
3And 165.37m
3, the pyrolysis oil productive rate is respectively 7.97% and 9.18%.Further No. 1 pyrolysis oil has been carried out rectifying under 185 ℃, the productive rate that draws light component and heavy component is respectively 35.86% and 64.14%.Pyrolysis Jiao's productive rate is respectively 65.33% and 61.66%, further pyrolysis Jiao has been carried out technical analysis, ultimate analysis and heating-value determination, and result is as shown in table 3.As seen the pyrolysis that makes of tail coal catalyse pyrolysis is burnt, and ash content slightly raises, and sulphur content has reduced by 25%, and the content of hydrogen and oxygen descends respectively more than 90%, and thermal value slightly raises, and is mainly because the small molecules fracture in tail coal, due to fixed carbon content increases.
Technical analysis and the results of elemental analyses of table 2 Fenxi tail coal
Table 3 Fenxi tail coal pyrolysis Jiao's technical analysis and results of elemental analyses
Claims (7)
1. a coking coal tail coal (coal slime) catalyse pyrolysis prepares the technique of clean fuel new technology, it is characterized in that utilizing tail coal (coal slime) preparation pyrolysis Jiao, pyrolysis gas and the pyrolysis oil of coking coal, and wherein pyrolysis Jiao can be used as the smokeless fuel use; Pyrolysis gas directly enters combustion chambers burn, for tail coal (coal slime) catalyse pyrolysis provides heat; Pyrolysis oil obtains light component and heavy component through rectifying separation, light component processing preparation flotation oil, and heavy component prepares oil in water emulsion after Over emulsfication, and oil in water emulsion enters combustion chambers burn, for tail coal (coal slime) catalyse pyrolysis provides heat.
2. catalyse pyrolysis technique according to claim 1, it is characterized in that tail coal (coal slime) at first is crushed to below 50mm, be sent in the feeding device with lock airway dysfunction by conveying belt, enter afterwards external-heat pyrolysis reaction unit catalyse pyrolysis, volatility product is through high-efficiency condensation, separation, reclaim pyrolysis liquid and pyrolysis gas, solid product enters in oke-quenching device via the discharge gate that is arranged at the bottom, reclaims pyrolysis Jiao after quenching.
3. according to claim 1 with 2 described coal slime catalyse pyrolysis techniques, complete on external-heat pyrolytic reaction device.This device comprises raw material crushing and delivery system, charging mixing system, external-heat reactive system, discharge and quench system, condensation and separation system, Controlling System.
4. external-heat reactive system according to claim 3 mainly forms by three layers, skin is the thermal insulation separation thermosphere, the centre is the pyrolytic reaction chamber, internal layer is the combustion chamber, the outer wall that combustion product gases directly enters the pyrolytic reaction chamber circulates, combustion chamber wherein is dual-fuel combustor, simultaneously the oil in water emulsion of combustion and pyrolysis gas and mink cell focus.
5. according to claim 1 with 2 described coking coal tail coal (coal slime) catalyse pyrolysis techniques, catalyzer system is put in coking coal tail coal (coal slime) in 0.5%～5.0% ratio by the adding set that is arranged on conveying belt, catalyzer is oxide compound or the mixture of basic metal, alkaline-earth metal, transition metal, can be also coal gangue, slag, lime-ash, industrial residue etc., wherein be suitable for the main chemical constitution of coal gangue, slag, lime-ash and the industrial residue used as tail coal (coal slime) catalyse pyrolysis, be generally Al
2O
31%～10%, SiO
21%～10%, Fe
2O
31%～70%, CaO5%～95%, MgO5%～90%, Na
2O1%～10%, K
2O1%～10%.
6. according to claim 1 with 2 described coking coal tail coal (coal slime) catalyse pyrolysis techniques, the temperature rise rate of pyrolytic reaction is controlled at 5 ℃ of-100 ℃/min, temperature of reaction is controlled between 820 ℃-950 ℃, pyrolysis time is controlled at 60～300min, and temperature rise rate and temperature of reaction can be regulated by the fuel quantity that control enters the combustion chamber.
7. according to claim 1,2 described coking coal tail coal (coal slime) catalyse pyrolysis techniques, it is characterized in that the low temperature pyrogenation stage, i.e. room temperature to 350 ℃, temperature rise rate is controlled at 5 ℃ of-30 ℃/min; In the warm solution stage, namely temperature is 380 ℃～800 ℃, temperature rise rate is controlled at 20 ℃ of-100 ℃/min; In the high temperature pyrolysis stage, namely temperature is 800 ℃～950 ℃, and temperature rise rate is controlled at 10 ℃ of-50 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110374284.7A CN103131443B (en) | 2011-11-23 | 2011-11-23 | Clean fuel new technology prepared by coking coal tail coal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110374284.7A CN103131443B (en) | 2011-11-23 | 2011-11-23 | Clean fuel new technology prepared by coking coal tail coal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103131443A true CN103131443A (en) | 2013-06-05 |
| CN103131443B CN103131443B (en) | 2015-12-16 |
Family
ID=48491904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110374284.7A Expired - Fee Related CN103131443B (en) | 2011-11-23 | 2011-11-23 | Clean fuel new technology prepared by coking coal tail coal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103131443B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232241A (en) * | 2014-10-13 | 2014-12-24 | 武汉科技大学 | Burning coal additive and preparation method thereof |
| CN113234511A (en) * | 2021-06-25 | 2021-08-10 | 中国矿业大学 | Lignite modification method and system for treating heavy metal wastewater |
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| WO1997038064A1 (en) * | 1996-04-10 | 1997-10-16 | Ilecard Pty. Ltd. | Process for treating coal tailings |
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2011
- 2011-11-23 CN CN201110374284.7A patent/CN103131443B/en not_active Expired - Fee Related
Patent Citations (3)
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|---|---|---|---|---|
| WO1997038064A1 (en) * | 1996-04-10 | 1997-10-16 | Ilecard Pty. Ltd. | Process for treating coal tailings |
| CN1814699A (en) * | 2005-02-05 | 2006-08-09 | 韩枫 | Boiler capable of producing jointly oil, gas and carbon and heat-energy by pyrolyzing biological fuels |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232241A (en) * | 2014-10-13 | 2014-12-24 | 武汉科技大学 | Burning coal additive and preparation method thereof |
| CN104232241B (en) * | 2014-10-13 | 2016-06-29 | 武汉科技大学 | A kind of additive for fire coal and preparation method thereof |
| CN113234511A (en) * | 2021-06-25 | 2021-08-10 | 中国矿业大学 | Lignite modification method and system for treating heavy metal wastewater |
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| Publication number | Publication date |
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| CN103131443B (en) | 2015-12-16 |
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