CN103740392B - The method of rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal - Google Patents
The method of rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 173
- 238000010438 heat treatment Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007669 thermal treatment Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 19
- 230000008676 import Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000004939 coking Methods 0.000 abstract description 15
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009997 thermal pre-treatment Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000021028 berry Nutrition 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- -1 small molecule hydrocarbon Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004079 vitrinite Substances 0.000 description 1
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Abstract
The invention provides a kind of method of rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal, belong to technical field of coal chemical industry.The coal charge that first granularity after drying is less than 3mm by the method by spiral vibration material feeder at top feed, enter rotating disc type thermal treatment unit after different atmosphere media preheating to certain temperature, the temperature rise rate that control furnace temperature and motor speed change coal charge comes upgrading low order weakly caking coal or low order non-caking coal.After thermal treatment, to be reduced to about 15%, H/C by original about 42% substantially unchanged for the dry ash-free basis volatile matter of coal sample, and the corresponding reduction of O/C is more, and after thermal treatment, coal sample volatile matter reduces obviously.Sticky to weak for the low order of high volatile (no) coal charge is deviate from part volatile matter by rotating disc type continuous heat treatment by the inventive method, and after upgrading, coal sample can add suitable proportion for coal-blending coking or be directly used in blast furnace pulverized coal injection.
Description
Technical field:
The invention belongs to technical field of coal chemical industry, be specifically related to a kind of method of rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal, the sticky coal of low order weak (no) processes part volatile matter through rotating disc type devolatilization, continuously then afterwards for coke making and coal blending or for blast furnace pulverized coal injection.
Background technology:
China is the country that coal usage ratio is the highest in the world, account for 27% of world's consumption of coal, although coal resources in China is abundanter, the reserves of low metamorphic grade bituminous coal (in long-flame coal, weakly caking coal, 1/2 sticky coal and non-caking coal) are very large, account for 32.6% of coal in China total reserves; But coking coal resource is relatively less, the reserves of medium metamorphic grade bituminous coal (rich coal, coking coal, 1/3 coking coal, gas-fat coal, bottle coal and lean coal) account for 26.3% of coal in China total reserves; In addition when national coke rush of demand, coking coal, rich coal due to stock number limited, supply is obviously becoming tight, and simultaneously part coking enterprise has started import coking coal.In this case, only have by expanding coking coal, Appropriate application non-coking coal resource is just very urgent.But it is more to the Grape berry method of low order weak (no) coal, its device mainly concentrates on above some fixed beds, air flow bed or blue charcoal stove etc., coal charge is directly become semicoke through medium temperature carbonization by these methods, limit its widespread use, therefore the coal charge of high volatile can be deviate from part volatile matter by the device of the sticky coal of rotating disc type continuous heat treatment low order of the present invention weak (no), improve its stuctures and properties, improve its utility value; Expand coking coal resource and stable coke quality, be applied to expand the new direction that coking coal resource and blast furnace pulverized coal injection become the research of low order non-caking coal.
The Grape berry method of coal sample has a lot, and wherein most study is the heat pre-treatment technique and hydrothermal pretreatment technique etc. of coal.
1, thermal pretreatment.Recent study finds to carry out thermal pretreatment to raw coal, can improve its cohesiveness, and to the exploration that its mechanism is correlated with.Therefore many investigators by carrying out Low Temperature Thermal upgrading to low order non-caking coal in fixed-bed reactor, to improving cohesiveness and the coking property of low order non-caking coal.Matsuura etc. think that rapid heating pre-treatment can increase the mobility of coal molecule particles and the slackness of coal molecule, after pre-treatment, the plasticity of coal sample strengthens, coke quality improves (Matsuura M.Testuto Hagane, 2003,89 (5): 565-572.).Dai Zhongshu etc. carry out low temperature pyrogenation to Datong coal and Yanzhou coal, and research finds that the activity of oxygen-containing functional group in coal is different, and therefore during thermal treatment, oxygen-containing functional group removes speed difference, thus causes the oxygen in coal to be reset; After Overheating Treatment, the micropore surface sum aperture of coal all increases (Dai Zhongshu etc., chemistry of fuel journal, 1999,27 (3): 256-261.) simultaneously.Because low-rank coal surface inserting is dispersed with more carboxyl, phenolic hydroxyl group isoreactivity oxygen-containing functional group, these content functional groups of low temperature pyrogenation remove, the O in coal molecule can be made to redistribute, and H distribution, C distribution and the change of pore size distribution, this is the reason place that low temperature pyrogenation causes coal molecular modification.
2, hydrothermal treatment consists.Coal sample is at different temperatures after hydrothermal treatment consists, found that extract content increases to some extent, the permanent good fortune of water etc. are (see " chemistry of fuel journal ", 2007, 35 (6): 655-659.) by testing Firing Shenhua Coal hydrothermal pretreatment, research finds that hydrothermal pretreatment can improve the vitrinite reflectance of coal, improve the swelling of Firing Shenhua Coal, the performance such as extracting and liquefaction, simultaneously along with hydrothermal treatment consists temperature raises, volatile matter reduces, ash content, H/C mol ratio all increases, and think water treatment coal sample under high pressure and high temperature, its non covalent bond structure can be destroyed, the generation being conducive to non covalent bond (with water) new in coal is added due to water, avoid the recombine of the non covalent bond destroyed in coal, thus improve coal extract content in a solvent, and along with the rising of water treatment temperature, the total quantity of the hydroxy functional group of coal sample constantly reduces, than few many time anhydrous.In water treatment procedure, the chemical bond rupture in the molecular network structure of coal, particularly hydrogen bond, the free radical of generation obtains hydrogen and stablizes, and its cohesiveness increases.（Mukherjee D,et al.1996.Fuel.75（4）：477）。
The above-mentioned thermal pretreatment technology to low order weakly caking coal or non-caking coal is all mainly carry out in fixed bed, coal charge is heated the technical problem underlying such as uneven, continuous treatment capacity is not enough in fixed bed, pretreated coal charge is much just transformed into semicoke, can cause the deficiencies such as the restriction in subsequent applications.The device of rotating disc type continuous heat treatment low order weakly caking coal of the present invention or low order non-caking coal just can solve these weak points, coal charge can be heated uniformly by this device, gaseous media after preheating enters from the bottom even distribution of device, with coal charge by cross-current flow flowing heat transfer, take pyrolysis gas out of, after pre-treatment, coal charge flows out from bottom, realizes continuous seepage.
Summary of the invention:
The present invention is directed to the technical problem existed in the sticky coal of existing process low order weak (no), a kind of method of rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal is provided, and coal charge after its upgrading can be added suitable proportion is used for coal-blending coking or is directly used in blast furnace pulverized coal injection.
The method of rotating disc type continuous heat treatment low order weakly caking coal provided by the present invention or low order non-caking coal, the method concrete steps are as follows:
(1) first low order weakly caking coal or low order non-caking coal are carried out drying treatment and obtain the coal charge that granularity is less than 3mm, then by described coal charge by the top feed of spiral vibration feeding machine at rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, be provided with sloping baffle uniform up and down and horizontal rotating disc uniform up and down, hot plate, thermopair, the opening for feed of spiral vibration feeding machine, bottom discharge mouth, the import of bottom heating gas, top pyrolysis gas outlet and motor in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device;
(2) described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device is entered from the import of described bottom heating gas by gas distributor by after gaseous media preheating, start rotating disc type continuous heat treatment low order weakly caking coal described in described driven by motor or low order non-caking coal device rotates continuously, the furnace temperature controlling described process furnace is the temperature range of 300 DEG C ~ 550 DEG C, regulate motor speed by described coal charge thermal treatment 15 ~ 40min in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, coal charge after being disposed is discharged from described bottom discharge mouth.
Described gaseous media is rare gas element (N
2, CO
2deng) or reducing gas (H
2, CH
4deng) or oxidizing atmosphere (air, H
2o(g) etc.), carrier gas flux is 0.1 ~ 1L/min, and the rotating speed of described motor is 5r/min ~ 30r/min.
The inventive method is by changing different all media, upgrading high-volatile low order weakly caking coal or low order non-caking coal under the conditions such as differing temps, namely under the atmosphere such as nitrogen and water vapour, granularity <3mm coal charge after drying is passed through spiral vibration material feeder at top feed, enter rotating disc type thermal treatment unit from bottom by gas distributor after different atmosphere media preheating to certain temperature, the temperature rise rate that the furnace temperature controlling process furnace changes coal charge in conditions such as 300 DEG C ~ 550 DEG C and motor speeds carrys out the sticky coal of upgrading low order weak (no); After thermal treatment, coal sample is provided with the optical signature of middle high-order coal, makes its V
dafabout 15% is reduced to by original about 42%; Infrared spectroscopy and functional group measure and show, the oxygen-containing functional group on coal sample structural unit and small molecules key there occurs fracture, and total acidic group and phenolic hydroxyl group decreasing ratio are about 50%.
Sticky to weak for the low order of high volatile (no) coal charge for raw material with the sticky coal of low order weak (no), is deviate from part volatile matter by rotating disc type continuous heat treatment, is improved its stuctures and properties, improve its utility value by the inventive method; And be applied to coal-blending coking or blast furnace pulverized coal injection.
Accompanying drawing illustrates:
Fig. 1: rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal apparatus structure schematic diagram.
In figure: 1: the opening for feed of spiral vibration charger, 2: sloping baffle, 3: horizontal rotating disc, 4: hot plate, 5: thermopair, 6: bottom discharge mouth, 7: the import of bottom heating gas, 8: top pyrolysis gas outlet.
Embodiment:
Implementing concrete grammar of the present invention is: raw material coal sample is the sticky coal of low order weak (no), granularity <3mm coal sample after drying is entered the low device of rotating disc type continuous heat treatment, adopts different atmosphere medium (rare gas element (N respectively
2, CO
2deng), reducing gas (H
2, CH
4deng), H
2o(g), oxidizing atmosphere (air)) etc., carrier gas flux is 0.1 ~ 1L/min, and the temperature rise rate that the furnace temperature (300 DEG C ~ 550 DEG C) controlling its indirect heating stove and motor speed change coal charge carrys out upgrading low order weak (no) and glues coal; And shown by Infrared spectroscopy and functional group's mensuration, the oxygen-containing functional group on coal sample structural unit and small molecule hydrocarbon key there occurs fracture, and total acidic group and phenolic hydroxyl group decreasing ratio are about 50%; After thermal treatment, coal sample is provided with the optical signature of middle high-order coal, can add suitable proportion for coal-blending coking or be directly used in blast furnace pulverized coal injection.
Embodiment 1: choose the sticky coal of high-volatile low order weak (no), coal sample essential property is as table 1, the coal charge of granularity <3mm after drying is passed through spiral vibration material feeder at top feed, rotating disc type thermal treatment unit is entered from bottom by gas distributor after inert atmosphere (nitrogen) is preheating to certain temperature, carrier gas flux is 0.5L/min, and the furnace temperature 400 DEG C controlling its indirect heating stove carrys out the sticky coal of upgrading low order weak (no) with motor speed 10 turns/min; Analytical results shows, after heat treatment, moisture significantly reduces, and is down to about 2.0% by original 10.3%; And along with the rising for the treatment of temp and slowing down of motor speed, moisture reduces larger; Dry ash-free basis volatile matter V
dafbe reduced to about 28.2% by original 42.9%, it is comparatively obvious to deviating from of oxygen-containing functional group; The carbon element content of process coal sample shows a rising trend substantially with the prolongation in treatment time and the rising for the treatment of temp, increases to about 80% from about 54% of raw coal; The rangeability of protium is less, does not substantially change.Illustrate according to above analysis of trend, the degree of coalification of thermal treatment coal sample increases.
Embodiment 2: choose the sticky coal of high-volatile low order weak (no), coal sample essential property is as table 1, and the coal charge of granularity <3mm after drying is passed through spiral vibration material feeder at top feed, heat-treating atmosphere adopts CO
2, treatment temp is 400 DEG C and motor speed 10 turns/min, and after thermal treatment, coal sample moisture is down to 1.8%; Dry ash-free basis volatile matter V
dafbe reduced to 30.1%, carbon element content increases to 75%.
Embodiment 3: choose the sticky coal of high-volatile low order weak (no), coal sample essential property is as table 1, the coal charge of granularity <3mm after drying is passed through spiral vibration material feeder at top feed, heat-treating atmosphere adopts water vapor, treatment temp is 450 DEG C and motor speed 10 turns/min, and after thermal treatment, coal sample moisture is down to 1.3%; Dry ash-free basis volatile matter V
dafbe reduced to 24%, carbon element content increases to 81%.
Embodiment 4: choose the sticky coal of high-volatile low order weak (no), coal sample essential property is as table 1, the coal charge of granularity <3mm after drying is passed through spiral vibration material feeder at top feed, heat-treating atmosphere adopts nitrogen, treatment temp is 450 DEG C and motor speed 10 turns/min, and after thermal treatment, coal sample moisture is down to 2.4%; Dry ash-free basis volatile matter V
dafbe reduced to about 20%, carbon element content increases to 77%.
Table 1 coal analysis data
Claims (3)
1. the method for rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal, is characterized in that the method concrete steps are as follows:
(1) first low order weakly caking coal or low order non-caking coal are carried out drying treatment and obtain the coal charge that granularity is less than 3mm, then by described coal charge by the top feed of spiral vibration feeding machine at rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, be provided with sloping baffle uniform up and down and horizontal rotating disc uniform up and down, hot plate, thermopair, the opening for feed of spiral vibration feeding machine, bottom discharge mouth, the import of bottom heating gas, top pyrolysis gas outlet and motor in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device;
(2) described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device is entered from the import of described bottom heating gas by gas distributor by after gaseous media preheating, start rotating disc type continuous heat treatment low order weakly caking coal described in described driven by motor or low order non-caking coal device rotates continuously, the furnace temperature controlling described process furnace is the temperature range of 300 DEG C ~ 550 DEG C, regulate motor speed by described coal charge thermal treatment 15 ~ 40min in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, coal charge after being disposed is discharged from described bottom discharge mouth.
2. the method for rotating disc type continuous heat treatment low order weakly caking coal according to claim 1 or low order non-caking coal, it is characterized in that described gaseous media is rare gas element or reducing gas or oxidizing atmosphere, carrier gas flux is 0.1 ~ 1L/min.
3. the method for rotating disc type continuous heat treatment low order weakly caking coal according to claim 1 or low order non-caking coal, is characterized in that the rotating speed of described motor is 5r/min ~ 30r/min.
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010090230A1 (en) * | 2009-02-03 | 2010-08-12 | 新日本石油株式会社 | Upgrading method for low-grade coal, and process for production of coke |
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Patent Citations (6)
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| CN101260307A (en) * | 2008-04-18 | 2008-09-10 | 清华大学 | Brown coal drying quality-increasing device and technique |
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