CN103740392A - Method for rotating disc type continuous heat treatment of low-order weakly caking coal or low-order non-caking coal - Google Patents
Method for rotating disc type continuous heat treatment of low-order weakly caking coal or low-order non-caking coal Download PDFInfo
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- CN103740392A CN103740392A CN201410030342.8A CN201410030342A CN103740392A CN 103740392 A CN103740392 A CN 103740392A CN 201410030342 A CN201410030342 A CN 201410030342A CN 103740392 A CN103740392 A CN 103740392A
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- 239000003245 coal Substances 0.000 title claims abstract description 175
- 238000010438 heat treatment Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims description 19
- 238000007669 thermal treatment Methods 0.000 claims description 11
- 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
- 238000001035 drying Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 15
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003039 volatile agent Substances 0.000 abstract 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
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000571 coke Substances 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
- 238000009997 thermal pre-treatment Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007812 deficiency 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 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
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 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
- 230000008961 swelling Effects 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 method for rotating disc type continuous heat treatment of low-order weakly caking coal or low-order non-caking coal, and belongs to the technical field of coal chemical industry. The method comprises the steps of feeding dried coal which is less than 3mm in granularity from top through a spiral vibrating feeder, preheating various atmosphere mediums to certain temperature and delivering to a rotating disc type heat treatment device, and changing heating rate of the coal through controlling furnace temperature and motor speed so as to modify low-order weakly caking coal or low-order non-caking coal. After heat treatment, volatiles of dry ash-free basis of the coal sample is reduced from original about 42% to about 15%, the coal sample is basically unchanged in H/C and correspondingly reduced in O/C, and the volatiles of the coal sample after heat treatment is obviously reduced. The method, disclosed by the invention, through rotating disc type continuous heat treatment, removes partial volatiles from low-order weakly caking (or non-caking) coal high in volatile content, and modified coal sample can be applied to coal blending for coking or directly used for blast furnace pulverized coal injection at a proper proportion.
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 continuously through rotating disc type devolatilization, then afterwards for coke making and coal blending or for blast furnace pulverized coal injection.
Background technology:
China is the highest country of coal usage ratio 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 (sticky coal and non-caking coal in long-flame coal, weakly caking coal, 1/2) 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; The in the situation that of national coke rush of demand, coking coal, rich coal are because stock number is limited in addition, and supply is obviously becoming tight, and part coking enterprise has started import coking coal simultaneously.In this case, only have by expanding coking coal, rationally utilize non-coking coal resource just very urgent.But more to the hot pretreatment process of (no) coal a little less than low order, its device mainly concentrates on above some fixed beds, air flow bed or blue charcoal stove etc., these methods directly become semicoke by coal charge through medium temperature carbonization, limit its widespread use, therefore the device of the sticky coal of rotating disc type continuous heat treatment low order of the present invention weak (no) can be deviate from part volatile matter by the coal charge of high volatile, improve its structure and performance, improve its utility value; Expansion coking coal resource and stable coke quality, be applied to expand coking coal resource and blast furnace pulverized coal injection becomes the new direction that low order non-caking coal is studied.
The hot pretreatment process of coal sample has a lot, and wherein most study is the heat pre-treatment technique of coal and hydrothermal pretreatment technique etc.
1, thermal pretreatment.Recent study finds raw coal to carry out thermal pretreatment, can improve its cohesiveness, and its mechanism has been carried out to relevant exploration.Therefore many investigators are by fixed-bed reactor, low order non-caking coal being carried out to Low Temperature Thermal upgrading, 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 particle and the slackness of coal molecule, after pre-treatment, the plasticity of coal sample strengthens, coke quality improve (Matsuura M.Testu to Hagane, 2003,89 (5): 565-572.).Dai Zhongshu etc. carry out low temperature pyrogenation to Datong coal and Yanzhou coal, and the activity difference of oxygen-containing functional group in coal is found in research, and therefore during thermal treatment, oxygen-containing functional group removes speed difference, thereby causes the oxygen in coal to be reset; After Overheating Treatment, the micropore surface of coal is long-pending simultaneously all increases (Dai Zhongshu etc., chemistry of fuel journal, 1999,27 (3): 256-261.) with aperture.Due to low-rank coal surface inserting distributing more carboxyl, phenolic hydroxyl group isoreactivity oxygen-containing functional group, these content functional groups of low temperature pyrogenation remove, can make the O redistribution in coal molecule, H distributes, C distributes and the variation of pore size distribution, and this is the reason place that low temperature pyrogenation causes coal molecular modification.
2, hydrothermal treatment consists.Coal sample under differing temps after hydrothermal treatment consists, found that extract content increases to some extent, the permanent good fortune of water etc. (is shown in < < chemistry of fuel journal > >, 2007, 35 (6): 655-659.) by Firing Shenhua Coal hydrothermal pretreatment is tested, 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, can destroy its non covalent bond structure, owing to being conducive to the generation of non covalent bond new in coal (with water) adding of water, avoided the recombine of the non covalent bond destroying in coal, thereby improve the extract content of coal in solvent, and along with the rising of water treatment temperature, the total quantity of the hydroxy functional group of coal sample constantly reduces, few many when 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）。
Above-mentioned is all mainly to carry out in fixed bed to the thermal pretreatment technology of low order weakly caking coal or non-caking coal, the coal charge technical problem underlying such as inhomogeneous, continuous treatment capacity deficiency of being heated in fixed bed, pretreated coal charge is much just transformed into semicoke, can cause the deficiencies such as the restriction aspect 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 distributes and enters from the bottom even of device, with coal charge by cross-flow mode flowing heat transfer, take pyrolysis gas out of, after pre-treatment, coal charge flows out from bottom, realizes continuously and producing.
Summary of the invention:
The present invention is directed to the technical problem existing in the sticky coal of existing processing 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 to suitable proportion 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 to drying treatment and obtain the coal charge that granularity is less than 3mm, then described coal charge is passed through to 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, in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, be provided with upper and lower uniform sloping baffle and upper and lower uniform horizontal rotating disc, the opening for feed that adds electrothermal stove, thermopair, spiral vibration feeding machine, bottom discharge mouth, the import of bottom heating gas, top pyrolysis gas outlet and motor;
(2) will after gaseous media preheating, from the import of described bottom heating gas, by gas distributor, enter described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, starting described in described driven by motor rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device rotates continuously, the furnace temperature of controlling described process furnace is the temperature range of 300 ℃～550 ℃, 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, under the atmosphere such as nitrogen and water vapour, after being dried, granularity <3mm coal charge passes through spiral vibration material feeder at top feed, different atmosphere media preheating enters rotating disc type thermal treatment unit from bottom by gas distributor after certain temperature, (no) sticky coal a little less than the temperature rise rate that the furnace temperature of controlling process furnace changes coal charge in conditions such as 300 ℃～550 ℃ and motor speeds carrys out upgrading low order; After thermal treatment, coal sample has had the optical signature of middle high-order coal, makes its V
dafby 42% original left and right, be reduced to 15% left and right; Infrared spectroscopy and functional group measure and show, fracture has occurred for the oxygen-containing functional group on coal sample structural unit and small molecules key, and total acidic group and phenolic hydroxyl group decreasing ratio are in 50% left and right.
The sticky coal of the inventive method (no) a little less than low order is raw material, by rotating disc type continuous heat treatment by the low order of high volatile a little less than (no) sticky coal charge deviate from part volatile matter, improve its structure and performance, improve its utility value; And be applied to coal-blending coking or blast furnace pulverized coal injection.
Accompanying drawing explanation:
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: add electrothermal stove, 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), and after being dried, granularity <3mm coal sample enters the low device of rotating disc type continuous heat treatment, adopts respectively different atmosphere medium (rare gas element (N
2, CO
2deng), reducing gas (H
2, CH
4deng), H
2o(g), oxidizing atmosphere (air)) etc., carrier gas flux is 0.1～1L/min, the furnace temperature (300 ℃～550 ℃) of controlling its indirect heating stove is carried out the sticky coal of upgrading low order weak (no) with the temperature rise rate that motor speed changes coal charge; And measure and show by Infrared spectroscopy and functional group, there is fracture in the oxygen-containing functional group on coal sample structural unit and small molecule hydrocarbon key, and total acidic group and phenolic hydroxyl group decreasing ratio are in 50% left and right; After thermal treatment, coal sample has had 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 dry is passed through to spiral vibration material feeder at top feed, after being preheating to certain temperature, inert atmosphere (nitrogen) enters rotating disc type thermal treatment unit from bottom by gas distributor, carrier gas flux is 0.5L/min, and 400 ℃ of furnace temperature controlling its indirect heating stove are carried out the sticky coal of upgrading low order weak (no) with turn/min of motor speed 10; Analytical results shows, after heat treatment, moisture significantly reduces, and by original 10.3%, is down to 2.0% left and right; 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 28.2% left and right by original 42.9%, it is comparatively obvious to deviating from of oxygen-containing functional group; The carbon element content of processing coal sample shows a rising trend substantially with the prolongation in treatment time and the rising for the treatment of temp, from 54% left and right of raw coal, increases to 80% left and right; The rangeability of protium is less, does not substantially change.According to above analysis of trend explanation, 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, as table 1, passes through spiral vibration material feeder at top feed by the coal charge of granularity <3mm after dry, and heat-treating atmosphere adopts CO
2, treatment temp is 400 ℃ and turn/min of motor speed 10, 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 dry is passed through to spiral vibration material feeder at top feed, heat-treating atmosphere adopts water vapor, treatment temp is 450 ℃ and turn/min of motor speed 10, 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 dry is passed through to spiral vibration material feeder at top feed, heat-treating atmosphere adopts nitrogen, treatment temp is 450 ℃ and turn/min of motor speed 10, and after thermal treatment, coal sample moisture is down to 2.4%; Dry ash-free basis volatile matter V
dafbe reduced to 20% left and right, 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 to drying treatment and obtain the coal charge that granularity is less than 3mm, then described coal charge is passed through to 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, in described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, be provided with upper and lower uniform sloping baffle and upper and lower uniform horizontal rotating disc, the opening for feed that adds electrothermal stove, thermopair, spiral vibration feeding machine, bottom discharge mouth, the import of bottom heating gas, top pyrolysis gas outlet and motor;
(2) will after gaseous media preheating, from the import of described bottom heating gas, by gas distributor, enter described rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device, starting described in described driven by motor rotating disc type continuous heat treatment low order weakly caking coal or low order non-caking coal device rotates continuously, the furnace temperature of controlling described process furnace is the temperature range of 300 ℃～550 ℃, 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, is characterized in that described gaseous media is rare gas element or reducing gas or oxidizing atmosphere, and 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, the rotating speed that it is characterized in that described motor is 5r/min～30r/min.
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2014
- 2014-01-22 CN CN201410030342.8A patent/CN103740392B/en not_active Expired - Fee Related
Patent Citations (7)
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| JP2759326B2 (en) * | 1988-10-27 | 1998-05-28 | 三菱化学株式会社 | Coke production method |
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