CN105478227A - Technology for achieving tar upgrading and iron reduction through catalytic pyrolysis of refractory iron ore to low-rank coal - Google Patents
Technology for achieving tar upgrading and iron reduction through catalytic pyrolysis of refractory iron ore to low-rank coal Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 105
- 239000003245 coal Substances 0.000 title claims abstract description 75
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title claims abstract description 16
- 238000007233 catalytic pyrolysis Methods 0.000 title abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 84
- 239000011269 tar Substances 0.000 claims abstract description 53
- 239000011280 coal tar Substances 0.000 claims abstract description 33
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007885 magnetic separation Methods 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 2
- 229910052595 hematite Inorganic materials 0.000 abstract 1
- 239000011019 hematite Substances 0.000 abstract 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- -1 rare earth compound Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 210000001113 umbilicus Anatomy 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/02—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge
- C10B47/06—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge in retorts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
In order to improve the coal pyrolysis tar quality of low-rank coal, reduce the content of heavy tar (with the boiling point being larger than 360 DEG C) and solve the problem that a catalyst is hard to recycle, a technology for achieving tar upgrading and iron reduction integration through catalytic pyrolysis of refractory iron ore to low-rank coal is achieved. Reducing ambinent of H2, Co and the like formed in the pyrolysis process are used for carrying out reduction on hematite in the iron ore to form magnetite while the refractory iron ore is used for carrying out catalytic pyrolysis on the low-rank coal to achieve coal tar upgrading, and furthermore magnetic recycling is carried out; and the technology is of important significance in low-rank coal pyrolysis utilization and refractory iron ore efficient recycling.
Description
Technical field
The present invention relates to one utilizes refractory iron ore to carry out catalyse pyrolysis to low-order coal, and the technology of coal tar upgrading and Fe3+ reduction is carried out in integration, belongs to coal chemical technology.
Background technology
At present, the main path of low-order coal processing and utilization is direct combustion power generation, liquefaction, gasification and middle low temperature pyrogenation etc., compared with other several processing and utilization approach, middle low temperature pyrogenation there is operating condition gentleness (normal pressure and in-condition such as low temperature), isolated air or use inert atmosphere, to feed coal without features such as strict demands.Low temperature pyrogenation in low-order coal, a considerable number of coal tar oil and gas can be produced, as clean energy resource or raw material, produce a large amount of active pyrolysis burnt simultaneously, for J. sigillate, or be used as blast furnace blowing fuel, be used for desulphurization and denitration process as adsorbent, also can carry out the standby clean gaseous fuel of vaporizing system and raw material further.
But research finds, pyrolysis gained coal tar mid-boiling point higher than the heavy components content of 360 DEG C up to more than 50%.Heavy component in tar is more, not only reduces the value of tar, and due to some heavy tars be easy to condensation, easily cause pipeline blockage, affect the stable operation of process system.Certainly, the higher application affecting pyrolytic technique to a certain extent of heavy component in tar.
In fact, some Small molecular groups in essence in coal of heavy component or the polycondensation in pyrolytic process of free radical fragment produce.Therefore, can regulate pyrolytic process by modes such as catalytic action completely, part changes pyrolytic reaction course, thus improves the quality of tar to a certain extent.
Much alkali (soil) metallic compound, transition metal and the pyrolytic process of rare earth compound to coal have catalytic action, can promote the pyrolysis process of coal.Particularly ferrum-based catalyst, is not only the dominant catalyst of DCL/Direct coal liquefaction, but also can improve tar yield and the oil quality of coal hydrogenation pyrolysis process.
As everyone knows, exploitation for many years, the many mines of China are composed and has a large amount of refractory iron ore, wherein be rich in bloodstone in many ores, if these refractory iron ores can be utilized, as the catalyst of low-order coal pyrolysis, while promotion pyrolysis of coal, by means of pyrolysis reduction atmosphere, to the Fe in refractory iron ore
2o
3reduce, form magnetic iron ore (Fe
3o
4), then reclaim iron ore concentrate by magnetic separation.That is, by the catalytic action of refractory iron ore, not only promote the pyrolytic process of low-order coal, and effectively can reclaim iron ore, to ensure the demand of steel industry stable development to iron ore, reduce the dependence to external iron ore to a certain extent.For this reason, the present invention explores and utilizes refractory iron ore to carry out catalyse pyrolysis to low-order coal, to realize the integration of tar upgrading and Fe3+ reduction.
This technology can make the removal efficiency of oxygen in tar reach 36.89%, and benzene homologues content improves 0.62%.The pyrolysis final temperature time of staying be 25min, under semicoke mog is that-0.074mm granularity accounts for 80.21%, magnetic field intensity is the condition of 96.48kA/m, to reducing iron ore magnetic separation in semicoke product, can obtain the iron ore concentrate that grade is 52.97%, the rate of recovery can reach 85.31%.
Summary of the invention
Based in the many refractory iron ores of China containing the feature of higher bloodstone, the present invention utilizes refractory iron ore as catalyst, by means of wherein Fe
2o
3catalytic action, promote the catalyse pyrolysis of low-order coal, carry out coal tar upgrading; Simultaneously by means of H in pyrolysis gas
2effect with the reducing atmosphere such as CO, is reduced into magnetic iron ore by the bloodstone in iron ore, then in addition magnetic separation is reclaimed.Carry out tar upgrading and Fe3+ reduction to realize the integration of refractory iron ore catalyse pyrolysis low-order coal, technical scheme of the present invention is as follows:
(1) refractory iron ore and low-order coal are crushed to-150 μm respectively, then add blender in the ratio of 0.5 ~ 49%:100% to mix, take appropriate amount of sample and be placed in fixed-bed pyrolysis reaction unit, be heat up within the scope of 5 ~ 100 DEG C/min at heating rate, pyrolysis is carried out, constant temperature 5 ~ 120min to pyrolysis final temperature in the scope being heated to 350 ~ 950 DEG C.
(2) pyrolysis gas produced in pyrolytic process carries out gas chromatographic analysis, analyzes aerogenesis composition and the change thereof of pyrolytic process.
(3) liquid of pyrolysis gained is weighed after total condensation, then take out the appropriate acetone and other organic solvent that adopts to dissolve, the tar separation that separatory funnel makes water and dissolves in acetone is adopted after dissolving, and then steam acetone by vacuum distillation method, separation obtains tar, then to weigh respectively, calculate respective content, the maximum relative deviation of tar yield is less than ± and 2%.
(4) pyrolysis Jiao is down to after room temperature until furnace temperature, and taking-up is weighed.The productive rate of pyrolysis three products can be obtained thus respectively, the maximum relative deviation of char yeild is less than ± and 5%, mass balance rate is between 95.1% ~ 97.9%.
(5) elementary analysis and GC-MS analysis are carried out to pyrolyzing coal tar, tentatively to determine element composition and the component composition of tar.
(6) pyrolysis Jiao being respectively 15min, 25min, 35min, 45min, 55min gained the time of staying under pyrolysis final temperature is milled to fineness and accounts for more than 50% for-0.074mm, being adjusted to pulp density is further 50%, then in low-intensity magnetic field field intensity is to carry out magnetic separation under the condition of 83.46kA/m, 96.48kA/m, 109.27kA/m, 125.88kA/m.By the rate of recovery of magnetic concentrate and the grade of iron ore concentrate, characterize refractory iron ore catalyse pyrolysis low-order coal to Fe in iron ore
2o
3reduction and Fe
3o
4recovery degree.
Accompanying drawing explanation
Fig. 1 is the change of low-order coal thermal decomposition product yield with temperature; Fig. 2 adds different proportion iron ore to the impact of low-order coal thermal decomposition product productive rate; Fig. 3 is the carbon number distribution of adding aliphatic hydrocarbon in coal tar that 20% iron ore generates during pyrolysis at 600 DEG C in low-order coal and coal; Fig. 4 is the carbon number distribution of adding benzene homologues in coal tar that 20% iron ore generates during pyrolysis at 600 DEG C in low-order coal and coal; Fig. 5 is the carbon number distribution of adding polycyclic aromatic hydrocarbon in coal tar that 20% iron ore generates during pyrolysis at 600 DEG C in low-order coal and coal; Fig. 6 adds the substituent carbon number distribution of phenolic material in coal tar that 20% iron ore generates during pyrolysis at 600 DEG C in low-order coal and coal; Fig. 7 is the component distribution adding the coal tar that 20% iron ore generates during pyrolysis at 600 DEG C in low-order coal and coal; Fig. 8 is the impact of reclaiming reducing iron ore magnetic separation the time of staying; Fig. 9 is the impact that mog reclaims reducing iron ore magnetic separation; Figure 10 is the impact that magnetic field intensity reclaims reducing iron ore magnetic separation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
Take 50g coal sample and add fixed-bed pyrolysis reaction unit, wherein coal sample moisture is 18.40% (air-dried basis), ash content is 4.72% (dry base), and volatilization is divided into 48.72% (dry ash free basis), fixed carbon is 51.28% (dry ash free basis).Carry out pyrolysis after being warming up to corresponding final temperature by the heating rate of 20 DEG C/min and stop 15min.The yield distribution of gained thermal decomposition product as shown in Figure 1.The change curve of char yeild under different temperatures as can be seen from Fig. 1, along with pyrolysis final temperature raises, char yeild declines.As can be seen from the change curve of different temperatures part of the body cavity below the umbilicus, housing the bladder, kidneys and bowels oil productive rate, tar yield reaches maximum 600 DEG C time, and declines to some extent 650 DEG C time, and corresponding gas-phase product productive rate raises along with temperature and raises.Because the productive rate of coal pyrolyzing coal tar 600 DEG C time is the highest, therefore, the pyrolysis final temperature of refractory iron ore catalyse pyrolysis low-order coal is defined as 600 DEG C, and the addition of iron ore is respectively 5%, 10%, 15%, 20%, 25% of coal sample quality.Wherein, all iron content, Al in iron ore
2o
3, SiO
2, CaO, content of MgO be respectively 41.43%, 4.80%, 26.53%, 4.35%, 3.27%.
The yield distribution of thermal decomposition product after different proportion iron ore is added as shown in Figure 2 in low-order coal.As shown in Figure 2, along with iron ore addition increases, char yeild declines gradually.When the addition of iron ore is 25%, char yeild is 55.57%.Tar yield also presents reduction trend along with the increase of iron ore addition, and when iron ore addition is less than 5%, its catalytic pyrolysis effect for coal tar is also not obvious; When addition is greater than 5%, iron ore shows the catalytic pyrolysis effect to tar gradually; When addition is 20 ~ 25%, the effect of catalytic pyrolysis is still subject to the impact of addition.The productive rate of pyrolysis gas and the addition correlation of iron ore, the more, the productive rate of pyrolysis gas is higher for the addition of iron ore, and when iron ore addition is 25%, the productive rate of gas is 24.45%.To sum up analyze and draw, the pyrolysis of iron ore to low-order coal has certain catalytic action, can impel the macromolecular compound generation second pyrolysis in tar, be converted into micromolecular gaseous material, reduces the productive rate of coal tar.Consider the consumption of the tar of iron ore catalyse pyrolysis low-order coal, gas yield and iron ore, select the addition 20% of iron ore to be advisable.With this understanding, the pyrolyzing coal tar obtained has carried out elementary analysis from raw coal pyrolytic tar under different pyrolysis final temperature, the results are shown in Table shown in 1.Can find out, add iron ore pyrolysis, to coal tar, there is certain deoxidation.When iron ore addition is
Pyrolytic tar elementary analysis under table 1 condition of different temperatures
When 20%, the oxygen content of pyrolytic tar is reduced to 8.70%, H/C ratio improves 0.36, O/C is reduced to 0.08 than by 0.14, oxygen removal rate is 36.89%, make the hydroxy derivatives in coal tar, namely various have the reduction of weakly acidic phenols content, improves stability and the use value of coal tar to a certain extent.
Embodiment 2
As seen from Figure 3, compared with the independent pyrolysis of raw coal, the aliphatic hydrocarbon content being greater than 20 carbon numbers after adding iron ore in pyrolysis of coal tar reduces, in interpolation iron ore pyrolytic tar, main chain is the content of 10 ~ 20 carbon number products is 9.20%, adds 5.00% than the product of 10 ~ 20 carbon numbers in raw coal pyrolytic tar.Illustrate in coal and add iron ore pyrolysis, aliphatic hydrocarbon main chain being greater than to 20 carbon numbers has catalytic pyrolysis effect, correspondingly improves the quality of tar.
As seen from Figure 4, in raw coal pyrolytic tar, the amount of tetramethyl substituting group (C4) benzene homologues is greater than the amount of adding after iron ore in pyrolysis of coal tar.The amount of adding dimethyl, trimethyl substituting group (C2, C3) benzene homologues in iron ore coal pyrolytic tar increases comparatively obvious, illustrate that adding iron ore carries out pyrolysis of coal, improve the content of more low carbon number substituting group (C2, C3) benzene homologues in pyrolytic tar, correspondingly improve the quality of tar.
As seen from Figure 5, the independent pyrolysis of coal and the pyrolysis of interpolation iron ore, in tar, two rings and tricyclic aromatic hydrocarbon content are all little, and the analysis of composition graphs 4 is known, and an aromatic hydrocarbon ring mainly comprises dihydroindene, indenes and homologue thereof.Add iron ore, the result of catalytic pyrolysis makes the content during pyrolysis independent higher than coal of the content of the dihydroindene in tar, indenes and homologue thereof, the pyrolysis of interpolation iron ore is described, correspondingly improves the quality of tar.
As can be seen from Figure 6, in tar, phenols main component is sylvan, dimethyl phenol, higher phenols.Add iron ore pyrolysis, in coal tar, the content of sylvan reaches 5.02%, improves 56.37% during pyrolysis more independent than coal.This illustrates and adds iron ore pyrolysis, remarkable to the splitting action of phenol in tar.Add iron ore pyrolysis, the amount when content of zero substituting group (C0) and methyl substituents (C1) phenols is greater than raw coal pyrolysis in coal tar in coal tar.Raw coal is respectively 4.63%, 4.55% with the content adding trimethyl substituting group (C3) phenolic material in iron ore pyrolytic tar, and tetramethyl substituting group (C4) phenolic material content is respectively 2.17%, 2.03%.This shows, add in coal iron ore pyrolysis in tar three, tetramethyl substituting group (C3, C4) phenols serves catalysis demethylation, improves the quality of tar.
As can be seen from Figure 7, in the independent pyrolysis liquids of coal, topmost component is oxygen-bearing organic matter, and its content is 31.52%; Next is aliphatic compound, and content is 26.72%; The content of polycyclic aromatic hydrocarbon is 12.90%; The content of phenols and benzene homologues is minimum, is respectively 12.56%, 3.98%.Along with the interpolation of iron ore, in pyrolysis of coal tar, aliphatic hydrocarbon content decreases, and in the coal tar that after adding iron ore, pyrolysis of coal produces, aliphatic hydrocarbon content reduces more obvious, reduces 2.54% compared to the aliphatic hydrocarbon content in raw coal tar; The content of phenols, compared to raw coal pyrolyzing coal tar, adds iron ore coal sample pyrolytic tar and increases 4.30%; Adding iron ore can make the content of benzene homologues in tar increase by 0.62%.Add iron ore and obviously can promote that in coal tar, polycyclic aromatic hydrocarbon content increases, and improves 2.20% compared to raw coal pyrolytic tar.Oxygenatedchemicals after adding iron ore in pyrolysis of coal tar then significantly reduces, and reduce 11.06%, this is consistent with the results of elemental analyses of tar.
In a word, along with iron ore adds, the phenols in pyrolytic tar and benzene homologues content raise, and benzene homologues content raises, and illustrate that adding of iron ore can promote long chain alkane in pyrolysis of coal tar or alkene generation cyclization.The minimizing of oxygen-bearing organic matter, illustrates that adding of iron ore can impel coal tar deoxidation, is conducive to the quality improving coal tar.
Embodiment 3
The pyrolysis obtained under being respectively 15min, 25min, 35min, 45min, 55min to pyrolysis final temperature 600 DEG C, interpolation iron ore 20%, the time of staying is burnt, be that-0.074mm accounts for 80%, low intensity magnetic separation field intensity has carried out magnetic separation separation under being the condition of 96.48kA/m in ore grinding pulp density 50%, fineness, the grade of gained iron ore concentrate and the relation of the pyrolysis final temperature lower time of staying after magnetic separation, as shown in Figure 8.As seen from Figure 8, along with extended residence time, the grade of magnetic concentrate first slowly rises and then slowly declines again.When the time of staying is 25min, grade reaches maximum 52.97%; The rate of recovery of iron ore, then from 78.01% during 15min, rapidly increases to 85.31% during 25min, after this starts again to decline.Therefore, the best bloodstone catalyse pyrolysis time of staying is approximately 25min.
Embodiment 4
Mog has a great impact magnetic separation product.Select interpolation 20% iron ore at 600 DEG C, stop pyrolysis Jiao of 25min, be under the condition of 96.48kA/m in low intensity magnetic separation field intensity, by the Task-size Controlling of-0.074mm in ore grinding sample between 54% ~ 93%, carried out magnetic separation test, result as shown in Figure 9.As can be seen from Figure 9, the grade of magnetic separation of iron ore concentrate first significantly increases along with mog increases, when-0.074mm content is greater than after 80%, and the grade kept stable of iron ore; When the content of-0.074m is 86.05%, grade reaches maximum 53.33%.The rate of recovery of iron ore concentrate then presents the trend of first increases and then decreases.Consider, the mog determining iron ore catalyse pyrolysis semicoke 80.21% carries out sorting for-0.074mm.
Embodiment 5
The field intensity of selection field also has a significant impact magnetic separation product.Choose exciting curent and be respectively 0.8A, 0.9A, 1.05A, 1.2A and 1.4A, corresponding magnetic field intensity is 74.68kA/m, 83.46kA/m, 96.48kA/m, 109.27kA/m, 125.88kA/m, pyrolysis of coal interpolation 20% iron ore being stopped at 600 DEG C to 25min is burnt, be under-0.074mm accounts for the condition of 80.21% at mog, carried out the experiment that field intensity affects magnetic separation, result as shown in Figure 10.Analysis draws, adds the grade of the burnt magnetic separation of iron ore concentrate of iron ore catalyse pyrolysis, and present downward trend along with magnetic field intensity increases, the rate of recovery then presents contrary trend.The rate of recovery of magnetic separation of iron ore concentrate increases less after magnetic field intensity 96.48kA/m, and grade then continues significantly to decline.Comprehensive analysis draws, sorting magnetic field intensity is 96.48kA/m is excellent.
Claims (7)
1. a refractory iron ore realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that utilizing refractory iron ore to carry out the catalyse pyrolysis of low-order coal, carrying out tar upgrading makes heavy component in coal tar reduce, simultaneously by means of CO and H in pyrolysis gas
2etc. reducing atmosphere, realize Fe in iron ore
2o
3reduction, formed Fe
3o
4, and then carry out magnetic separation recovery.
2. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, described low-order coal refers to V
dafthe coal of the low metamorphic grade of>=30%.
3. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, described refractory iron ore refers to that bloodstone or higher other of bloodstone content are difficult to the iron ore with magnetic separation technology sorting, even mine tailing.
4. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, the mass ratio that the addition of described refractory iron ore accounts for coal is 0.5 ~ 49%.
5. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, pyrolysis final temperature is 350 ~ 950 DEG C, and the time of staying is 5min ~ 120min.
6. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, during pyrolysis Jiao magnetic separation, mog is advisable for-0.074mm particle accounts for more than 50.
7. a kind of refractory iron ore according to claim 1 realizes the technology of tar upgrading and Fe3+ reduction to low-order coal catalyse pyrolysis, it is characterized in that, during pyrolysis Jiao magnetic separation, field intensity selects 10 ~ 200kA/m to be advisable.
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