CN103952184B - Catalytic coal gasifaction prepares the method and system of shaft furnace reducing gases - Google Patents
Catalytic coal gasifaction prepares the method and system of shaft furnace reducing gases Download PDFInfo
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- CN103952184B CN103952184B CN201410204168.4A CN201410204168A CN103952184B CN 103952184 B CN103952184 B CN 103952184B CN 201410204168 A CN201410204168 A CN 201410204168A CN 103952184 B CN103952184 B CN 103952184B
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- 239000007789 gas Substances 0.000 title claims abstract description 288
- 230000001603 reducing effect Effects 0.000 title claims abstract description 216
- 239000003245 coal Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 81
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000002309 gasification Methods 0.000 claims abstract description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002918 waste heat Substances 0.000 claims abstract description 56
- 238000000197 pyrolysis Methods 0.000 claims abstract description 50
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000005338 heat storage Methods 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 23
- 238000006477 desulfuration reaction Methods 0.000 claims description 22
- 230000023556 desulfurization Effects 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 21
- 230000008676 import Effects 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- -1 amino-compound Chemical compound 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 27
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 39
- 238000000926 separation method Methods 0.000 description 28
- 230000003009 desulfurizing effect Effects 0.000 description 22
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 21
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 21
- 238000005201 scrubbing Methods 0.000 description 19
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001465 metallisation Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 241001417490 Sillaginidae Species 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Industrial Gases (AREA)
Abstract
The invention discloses catalytic coal gasifaction and prepare the method and system of shaft furnace reducing gases, wherein, catalytic coal gasifaction is prepared the method for shaft furnace reducing gases and is included: carry out pressure ball process with catalyst after being mixed by fine coal, in order to obtain pulverized coal particle；Pulverized coal particle and steam is made to occur catalytic gasification to react under the effect of catalyst in heat storage type pyrolysis stove, in order to generate containing hydrogen, carbon monoxide, carbon dioxide and the thick reducing gases of hydrogen sulfide；Thick reducing gases is carried out waste heat recovery, in order to produce steam；Thick reducing gases through waste heat recovery is carried out purification processes, in order to obtain refined reducing gases.Utilizing said method can reduce gasification temperature, save energy consumption, the reducing gases prepared can reach the gas-based shaft kiln refining sponge iron requirement to reducing gases.
Description
Technical field
The present invention relates to a kind of gas-based shaft kiln reducing gases preparation technology, the coal particularly producing sponge iron supporting with gas-based shaft kiln is urged
Activating QI prepares the method and system of shaft furnace reducing gases.
Background technology
Direct reduction processes of Iron ores mainly has gas base (with CO+H2For reducing agent) and coal base (with mill coal as reducing agent)
Two kinds.Gas base directly reducing method because having that capacity utilization is high, the thermal efficiency high, productivity ratio advantages of higher and become mill coal smelting
The mainstream technology of gold process.
At present, the mode of external multiplex gas renormalizing reducing gases provides CO+H2As reducing gases.Compared with abroad, by
In being limited by natural gas resource, China does not has large-scale shaft furnace process to produce direct-reduction ironworks so far.Comparatively speaking,
Rich coal resources in China, the level of resources utilization of coal is the most relatively low, if deep purifying desulfurization process will be carried out after coal gasification
As unstripped gas, then mix with appropriate steam etc., enter change furnace and carry out transformationreation and i.e. can get H2The ratio of/CO exists
H between 4.6～1.5:1 (volume ratios)2Gaseous mixture with CO.This gaseous mixture can produce sponge as direct-reduction
The reducibility gas of ferrum, and there is the advantages such as cheap.
At present, the gasification temperature of the coal gasifying process of comparative maturity is typically more than 1000 DEG C, and along with the development of coal gasification,
Coal gasifying process increasingly approaches the prior art limit of High Temperature High Pressure, in order to promotes gasification reaction to greatest extent, thus sends out
Wave large-scale production effect.Along with gasification temperature increases, need to consume more coal to maintain high-temperature gasification state and raw
The gas products of output is high due to temperature, can more bring more energy loss, the simultaneously CO in coal gas in temperature-fall period
Content is the highest, in the technique of producing synthesis gas or hydrogen, it is necessary to converted by CO, causes complex energy utilization ratio
Lowly, these technique produces synthesis gas and is both needed to pure oxygen participation reaction simultaneously, and the preparation of pure oxygen needs expensive air separation plant throwing
Money and higher preparation cost, become the Main Bottleneck of restriction coal gasification, have impact on the competitiveness of Coal Chemical Industry, and therefore high temperature is high
The coal gasification of pressure is not necessarily optimized gasification mode.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the one of the present invention
Purpose is to propose a kind of method that catalytic coal gasifaction prepares shaft furnace reducing gases, and it is low that the method has gasification temperature, gasification effect
Rate is high, to advantages such as the requirement of equipment material are low.
Catalytic coal gasifaction according to embodiments of the present invention prepares the method for shaft furnace reducing gases, including:
Pressure ball process is carried out with catalyst, in order to obtain pulverized coal particle after being mixed by fine coal；
Make described pulverized coal particle react with steam generation catalytic gasification in heat storage type pyrolysis stove, in order to generate containing hydrogen,
The thick reducing gases of carbon monoxide, carbon dioxide and hydrogen sulfide；
Described thick reducing gases is carried out waste heat recovery, in order to produce steam；
Thick reducing gases through described waste heat recovery is carried out purification processes, in order to obtain refined reducing gases,
Wherein, in described refined reducing gases the total content of hydrogen and carbon monoxide for being not less than 88 volume %, described hydrogen and institute
The volume ratio stating carbon monoxide is (3.5～1.5): 1；The oxidizability of described refined reducing gases is less than 5%；
The reaction of described catalytic gasification is to carry out under the pressure of 650～800 degrees Celsius and 22KPa.
Thus, the method that the catalytic coal gasifaction of the above embodiment of the present invention prepares shaft furnace reducing gases is simply efficient, and energy consumption is low,
Not only environmental protection but also qualified spongy iron reducing gas can be produced at low cost, whole technique is that environmental protection and energy saving are feasible technically,
It it is a kind of method efficiently utilizing coal reducing gases.
It addition, the method that catalytic coal gasifaction according to the above embodiment of the present invention prepares shaft furnace reducing gases can also have as follows
Additional technical characteristic:
In some embodiments of the invention, the mass ratio of described fine coal, catalyst and steam is: (1～4): (0.01～0.08):
1.Thus so that the reducing gases prepared meets gas-based shaft kiln prepares the sponge iron requirement to reduction.
In some embodiments of the invention, the described water vapour described waste heat recovery produced returns and is used for described catalytic gasification
Reaction.Thus can save energy consumption further.
In some embodiments of the invention, described purification processes includes:
Thick reducing gases through described waste heat recovery is carried out carrying out washing treatment, in order to remove the catalysis of residual in described thick reducing gases
Agent and fine ash；
Thick reducing gases through described carrying out washing treatment is carried out desulfurization process, in order to remove hydrogen sulfide gas；
It is compressed the thick reducing gases processed through described desulfurization processing；And
The thick reducing gases processed through described compression is carried out carbonization treatment, in order to remove carbon dioxide and obtain described refined reduction
Gas.Thus can improve the purity of reducing gases further, improve the hydrogen of reducing gases and the volume ratio of carbon monoxide.
In some embodiments of the invention, described desulfurization process and carbonization treatment all use N methyldiethanol amine to carry out.By
This can improve desulfurization and decarburization efficiency and effect further.
Therefore, for the deficiency of existing Coal Gasification Technology technique, the present invention uses the catalytic gasification technology of coal to replace existing
Coal Gasification Technology prepares the reducing gases needed for gas-based shaft kiln, and in the case of adding catalyst, pulverized coal particle can be 650～800
The reaction of rapid generating gasification, H in the crude synthesis gas of generation under degree Celsius2The ratio of/CO, between 3.5～1.5:1, meets
The requirement of gas-based shaft kiln reducing gases, and it is made without conversion；The interpolation of catalyst reduce the temperature of coal gasification, energy consumption and
Requirement to equipment material etc., and the most highly beneficial to desulfurization, dedusting and environmental protection etc., coal gas composition in product is had more preferably
Selectivity, further, since during need not oxygen, without nitrogen in synthesis gas, improve industrial economy
Property.
According to another aspect of the present invention, the present invention proposes a kind of catalytic coal gasifaction and prepares the system of shaft furnace reducing gases.
Catalytic coal gasifaction according to embodiments of the present invention prepares the system of shaft furnace reducing gases, it is characterised in that including:
Heat storage type pyrolysis stove, described heat storage type pyrolysis stove has fine coal catalyst granules import, water vapour import and thick reducing gases
Outlet, described heat storage type pyrolysis stove is suitable to fine coal, water vapour and occurs catalytic gasification to react under the effect of catalyst, in order to raw
Become containing hydrogen, carbon monoxide, carbon dioxide and the thick reducing gases of hydrogen sulfide；
Waste heat boiler, described waste heat boiler has thermal reduction gas import, the outlet of cold reducing gases and steam (vapor) outlet, described thermal reduction
Gas import is connected with the outlet of described thick reducing gases, and described waste heat boiler is suitable to described thick reducing gases is carried out waste heat recovery, in order to
Produce steam；
Purifying plant, described purifying plant is connected with described waste heat boiler, and described purifying plant is suitable to return through described waste heat
The thick reducing gases received carries out purification processes, in order to obtain refined reducing gases.
It addition, the system that catalytic coal gasifaction according to the above embodiment of the present invention prepares shaft furnace reducing gases can also have as follows
Additional technical characteristic:
In some embodiments of the invention, the described steam (vapor) outlet of described waste heat boiler and described heat storage type pyrolysis stove is described
Water vapour import is connected, in order to described steam is used for the reaction of described catalytic gasification.Thus can save energy consumption further.
In some embodiments of the invention, what described purifying plant included being sequentially connected is suitable to return through described waste heat described
The thick reducing gases received carries out carrying out washing treatment, desulfurization process, compression process and the washing facility of carbonization treatment, desulphurization plant,
Compression device and decarbonation appliance.
Accompanying drawing explanation
Fig. 1 is the flow chart that the catalytic coal gasifaction according to one embodiment of invention prepares the method for shaft furnace reducing gases.
Fig. 2 is the flow chart of the method preparing shaft furnace reducing gases according to the catalytic coal gasifaction inventing another embodiment.
Fig. 3 is the structural representation that the catalytic coal gasifaction according to one embodiment of invention prepares the system of shaft furnace reducing gases.
Fig. 4 is the structural representation of the system preparing shaft furnace reducing gases according to the catalytic coal gasifaction inventing another embodiment.
Fig. 5 is the structural representation of the system preparing shaft furnace reducing gases according to the catalytic coal gasifaction inventing another embodiment.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most identical
Or similar label represents same or similar element or has the element of same or like function.Retouch below with reference to accompanying drawing
The embodiment stated is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
Below with reference to Fig. 1-2, the method that the catalytic coal gasifaction of the embodiment of the present invention prepares shaft furnace reducing gases is described.
Catalytic coal gasifaction according to embodiments of the present invention is prepared the method for shaft furnace reducing gases and is included:
S100: catalytic gasification reacts
Pressure ball process is carried out with catalyst, in order to obtain pulverized coal particle after being mixed by fine coal；
Pulverized coal particle is made to react with steam generation catalytic gasification in heat storage type pyrolysis stove, in order to generate containing hydrogen, an oxygen
Change carbon, carbon dioxide and the thick reducing gases of hydrogen sulfide.
Thus, utilize water vapour as gasifying agent and to make use of catalyst to carry out catalytic coal gasifaction, gasification reaction can be reduced
Temperature, it is not necessary to maintain the temperature of gasification furnace with air burning part coal, so can avoid being brought into nitrogen by air, closes
Become in gas without nitrogen, it is to avoid follow-up nitrogen separation problem, improve FU and mention being suitable for of disposal ability and coal
Property, energy efficient expense, avoid being brought into nitrogen by air simultaneously and can reduce the thermal loss of system, reduce equipment investment
And production cost.The low-temperature catalysis gasification of coal make pulverized coal particle and steam under the effect of catalyst, in relatively low temperature
Under can carry out gasification reaction, reduce the temperature of coal gasification, energy consumption and the requirement to equipment material etc., and to desulfurization,
Dedusting and environmental protection etc. are the most highly beneficial.
Use the fine coal after pressure ball to prepare reducing gases and can save the pneumatic conveyer of configuration fine coal, and then Simplified flowsheet reduces
Equipment cost.According to a particular embodiment of the invention, pressure ball processes the particle diameter of the pulverized coal particle obtained can be 10～50mm.
Process the contact area that can increase fine coal with catalyst from there through pressure ball, and then charcoal percent conversion can be significantly improved, with
Time pressure ball to obtain particle diameter be that 10～50mm pulverized coal particles are possible not only to eliminate the need for pneumatic conveyer conveying fine coal, improve simultaneously
Steam is more prone to and pulverized coal particle contact area.Although the particle diameter of fine coal is less, but when contacting with steam, water steams
Gas is extremely difficult to contact with all fine coal, and therefore gasification efficiency is the highest.But fine coal and catalyst are pressed into pelletizing in advance
And then steam contact can increase steam and pelletizing touch opportunity on the contrary, and then gasification efficiency can be significantly improved.
According to a particular embodiment of the invention, the mass ratio of fine coal, catalyst and steam is: (1～4): (0.01～0.08):
1, thus can improve gasification efficiency, energy efficient further, and by using reducing gases that said ratio prepares
H2/CO2The requirement of the reducing gases of gas-based shaft kiln sponge iron smelting can be reached.Therefore, fine coal, steam and catalyst are pressed
Carry out catalytic gasification reaction according to above-mentioned quality proportioning, gasification reaction efficiency can be improved further, improve the productivity of reducing gases.
According to a particular embodiment of the invention, the interpolation of catalyst can make the gasification at low temperatures of fine coal, coal gasification simultaneously
The methane generated divides under the effect of catalyst and react production carbon monoxide and hydrogen further with steam, pulverized coal pyrolysis generation
Coal tar under the effect of catalyst, be also carried out twice decomposition, create more reducing gases.The conversion of methane and coal tar
Twice decomposition carry out in same reactor, be greatly improved the efficiency of process, catalyst can also absorb part sulfur simultaneously
Change low temperature gasification and the desulfurization of postorder, dedusting and the environmental protection of the gas such as hydrogen and carbon dioxide, beneficially coal, and to reducing gases
Composition has more preferable selectivity.
According to a particular embodiment of the invention, catalyst be selected from alkali metal, transition metal, alkaline-earth metal at least one
Oxide or salt, wherein, alkali metal is selected from least one of lithium, sodium, potassium, rubidium and cerium；Transition metal be vanadium, chromium,
At least one of manganese, ferrum, cobalt, nickel, copper and molybdenum；Alkaline-earth metal is at least one of magnesium, calcium and barium；The type of salt is carbon
Hydrochlorate, sulfate, heavy carbonate, formates, oxalates, amino-compound, hydroxide, acetate at least one.
Thus, the addition of catalyst can improve gasification reaction efficiency further, reduces the temperature of coal gasification, energy consumption and to equipment
The requirement of material etc., it is also possible to absorb the gases such as the partial vulcanization hydrogen in thick also one-tenth gas and carbon dioxide, be conducive to operation the most below
Desulfurization, dedusting and environmental protection.And the composition to thick reducing gases that adds of catalyst has more preferable selectivity.
According to another embodiment of the invention, in above-mentioned catalyst containing 0.1～3.0 weight % alkaline-earth metal oxide and
/ or the salt of alkaline-earth metal.Thus can significantly improve catalytic efficiency, can be by carbon for example with the catalyst with said components
Conversion ratio brings up to 90% from 54%, and the content of hydrogen and carbon monoxide increases to 89% from 44%.Concrete according to the present invention
Embodiment, above-mentioned alkaline-earth metal is specifically as follows at least one of magnesium, calcium and barium.Thus can significantly improve urging of catalyst
Change efficiency, improve efficiency of carbon con version and the content of reducing gas.
According to another specific embodiment of the present invention, the bar of the catalytic gasification reaction of above-mentioned carrying out in heat storage type pyrolysis stove
Part is not particularly restricted, and according to the concrete example of the present invention, the reaction of above-mentioned catalytic gasification can be at 650～800 degrees Celsius
With carry out under the pressure of 22KPa.
Traditional coal gasification reaction need 1200～1500 degrees Celsius and 2～6MPa pressure under carry out, even if use
Catalyst, the pressure of its gasification reaction also to control 3～4MPa.Therefore the catalytic coal gasifaction of the present invention prepares shaft furnace with also
The method more existing coal gasification reaction of Primordial Qi save considerably energy consumption.According to a particular embodiment of the invention, by utilizing
The reducing gases that said method prepares can reach gas-based shaft kiln and prepare the requirement of sponge iron.
S200: waste heat recovery
According to a particular embodiment of the invention, thick reducing gases obtained above is carried out waste heat recovery, in order to produce steam.
While thus can reclaiming heat, thick reducing gases is lowered the temperature.
According to another specific embodiment of the present invention, the water vapour produced can be returned and be used for catalytic gasification in waste heat boiler
Reaction.Thus can save the energy consumption preparing steam.
S300: purification processes
According to a particular embodiment of the invention, further the thick reducing gases through waste heat recovery is carried out purification processes, in order to
Obtain refined reducing gases.Thus can improve the purity of reducing gases, and obtain that there is suitable H2/CO2The refined reduction of proportioning
Gas.
According to a particular embodiment of the invention, as in figure 2 it is shown, purification processes may further include:
S310: carrying out washing treatment
According to a particular embodiment of the invention, first the thick reducing gases through waste heat recovery is carried out carrying out washing treatment, in order to remove
The catalyst remained in thick reducing gases and fine ash.
According to the concrete example of the present invention, carrying out washing treatment can specifically be carried out according to the following step, by thick reducing gases with carry out self-excitation
The water flow through venturi of water supply pump mixes, and fine ash is soaked completely by water, and the most scrubbed tower down-comer enters wash tower bottoms water
Bath, removes remaining fine ash, and then the annular space through between down-comer and airway rises, and enters the column plate at scrubbing tower top, logical
Cross the demister above column plate to be separated by the water droplet carried secretly.It is substantially free of the thick reducing gases of fine ash to go out scrubbing tower and deliver to take off
Sulfur tower.The acid solution discharged at the bottom of scrubbing tower enters catalyst reclaimer, reclaims catalyst.
S320: desulfurization processes
According to the concrete example of the present invention, the thick reducing gases through carrying out washing treatment is carried out desulfurization process, in order to remove hydrogen sulfide
Gas.
According to a particular embodiment of the invention, desulfurization processes and N methyldiethanol amine can be used to carry out.Thus can be further
Improve desulfurized effect, specifically can the slightly H in reducing gases2S is from 4g/m3Take off 2mg/m3.And use N-methyl diethanol
Amine can also remove considerable amount of CO while removing hydrogen sulfide2, thus can improve hydrogen and an oxygen in reducing gases further
Change the total content of carbon, improve reducing gases reducing property.Therefore, the catalytic coal gasifaction preparation using the above embodiment of the present invention is perpendicular
The method of stove reducing gases prepares reducing gases and is used directly for gas-based shaft kiln smelting sponge iron, and can significantly improve
The quality of sponge iron and efficiency.
According to the concrete example of the present invention, desulfurization processes and can specifically carry out according to the following step, the scrubbed process of thick reducing gases
Entering after dedusting cooling bottom desulfurizing tower, top-down MDEA solution ((N methyldiethanol amine)) adverse current connects with in tower
Touch and absorb overwhelming majority H2S and part SO2And COS.The reducing gases entrance tower top cooler going out desulfurizing tower is cooled to 40 DEG C of left sides
The right side, enters gas-liquid separator and carries out gas-liquid separation, reclaim MDEA absorbing liquid (N methyldiethanol amine), about 22kPa (G)
Reducing gases deliver to compressor 1.The rich solution discharged at the bottom of desulfurizing tower, enters flash tank flash distillation through rich solution pump, flash drum overhead
CO is entered after flash steam is condensed together with the flash steam of decarbonization section and the tower overhead gas of solution regenerator2Separator and desulfurizer.
Sulfur in desulfurizer after treatment, produces and sells outside sulfur, and the lean solution after regeneration at the bottom of regenerator tower is cold through solution heat exchanger and solution
But desulfurizing tower and decarbonizing tower recycling are returned after device heat exchange and cooling.
S330: compression processes
According to a particular embodiment of the invention, it is compressed the thick reducing gases processed through desulfurization processing.According to the present invention's
Concrete example, it is possible to use reducing gases is compressed to 1MPa (G) left and right by compressor, then draws into decarbonizing tower.
S340: carbonization treatment
The thick reducing gases processed through described compression is carried out carbonization treatment, in order to remove carbon dioxide and obtain described refined reduction
Gas.
According to a particular embodiment of the invention, carbonization treatment can use N methyldiethanol amine to carry out.
According to the concrete example of the present invention, desulfurization processes and can specifically carry out according to the following step, makes the reduction from compressor
Gas enters air inlet grease trap, laggard decarbonizing tower, reducing gas bottom in and top out, absorbing liquid MDEA upper entering and lower leaving, counter current contacting.
Gas after decarburization by tower top out, enters tower top cooler, the reducing gas heated up because of absorption is cooled to 40 DEG C, passes through
Fine decarbonization tower liquid/gas separator of working off one's feeling vent one's spleen carries out gas-liquid separation, reclaims MDEA absorbing liquid.The desulfurizing tower processed from desulfurization is with de-
Flash tank is entered after two bursts of MDEA (N methyldiethanol amine) solution mixing of the decarbonizing tower that carbon processes.Flash drum overhead goes out
CO is entered after next flash steam is condensed together with the tower overhead gas of regenerator2Separator and desulfurizer, the sulfur in desulfurizer is through place
After reason, produce and sell outside sulfur；Lean solution after regeneration at the bottom of regenerator tower is returned after solution heat exchanger and solution cooler heat exchange cool down
Return above-mentioned desulfurizing tower and decarbonizing tower recycles.
According to a particular embodiment of the invention, by using hydrogen and an oxidation in the refined reducing gases for preparing of said method
The total content of carbon is for being not less than 88 volume %, and hydrogen is (3.5～1.5) with the volume ratio of carbon monoxide: 1.Therefore this is refined also
Primordial Qi can reach gas-based shaft kiln and prepare the sponge iron requirement to reducing gases.According to a particular embodiment of the invention, by above-mentioned
The oxidizability of the refined reducing gases that method prepares is less than 5%, pressure about 1.0MPa (G).And then utilize this refined reducing gases
Ironmaking, can improve degree of metalization, productivity ratio and capacity usage ratio further, improves the purity of ferrum and reduces energy consumption.
Describe the catalytic coal gasifaction of the embodiment of the present invention below with reference to Fig. 3-4 and prepare the system of shaft furnace reducing gases.
Catalytic coal gasifaction according to embodiments of the present invention is prepared the system 100 of shaft furnace reducing gases and is included: heat storage type pyrolysis stove 10,
Waste heat boiler 20 and purifying plant 30.
Wherein, heat storage type pyrolysis 10 stove has fine coal catalyst granules import 11, water vapour import 12 and thick reducing gases outlet
13, heat storage type pyrolysis stove is suitable to fine coal, water vapour and occurs catalytic gasification to react under the effect of catalyst, in order to generates and contains
The thick reducing gases of hydrogen, carbon monoxide, carbon dioxide and hydrogen sulfide；
Waste heat boiler 20 has thermal reduction gas import 21, a cold reducing gases outlet 22 and steam (vapor) outlet 23, thermal reduction gas import with
The outlet of described thick reducing gases is connected, and waste heat boiler is suitable to thick reducing gases is carried out waste heat recovery, in order to produce steam；
Purifying plant 30 has cold reducing gases import 301 and refined reducing gases outlet 302, cold reducing gases import 301 and waste heat
The cold reducing gases outlet 22 of boiler is connected, and purifying plant is suitable to the thick reducing gases through waste heat recovery is carried out purification processes, with
Just refined reducing gases is obtained.
As shown in Figure 4, according to a particular embodiment of the invention, the institute of the steam (vapor) outlet 23 of waste heat boiler and heat storage type pyrolysis stove
State water vapour import 12 to be connected, in order to steam is used for catalytic gasification reaction.Thus can save the energy consumption preparing steam.
According to a particular embodiment of the invention, what what purifying plant farther included to be sequentially connected be suitable to through waste heat recovery is thick
Reducing gases carries out the washing facility 31 of carrying out washing treatment, desulfurization process, compression process and carbonization treatment, desulphurization plant 32, pressure
Contracting equipment 33 and decarbonation appliance 34.Thus thick reducing gases can be purified and then obtains refined reducing gases.According to this
Bright specific embodiment, by using above-mentioned catalytic coal gasifaction to prepare the refined reduction that the system of shaft furnace reducing gases prepares
In gas, the total content of hydrogen and carbon monoxide is for being not less than 88 volume %, and hydrogen is (3.5～1.5) with the volume ratio of carbon monoxide:
1.Therefore this refined reducing gases can reach gas-based shaft kiln and prepares the requirement of sponge iron.According to a particular embodiment of the invention, essence
The oxidizability of reducing gases processed is less than 5%, pressure about 1.0MPa (G).And then utilize this refined reducing gases to smelt iron, can be further
Improve degree of metalization, productivity ratio and capacity usage ratio, improve the purity of ferrum and reduce energy consumption.
Embodiment 1
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.06 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-14.5%FeCl3-1.5%Ca (Ac)2；By powder
Coal particle adds in heat storage type pyrolysis stove, and is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to
2.5kg:1kg proportioning in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure be about 22KPa
Under conditions of in heat storage type pyrolysis stove reaction generate thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The mixing of S etc.
Gas).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 94%, and in product, hydrogen and carbon monoxide contains
Amount is 92%, and the ratio of hydrogen and carbon monoxide is 3.8:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 93%.
Embodiment 2
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.06 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-14.5%FeCl3-1.5%BaCl2；By fine coal
Granule adds in heat storage type pyrolysis stove, and is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to
2.5kg:1kg proportioning in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure be about 22KPa
Under conditions of in heat storage type pyrolysis stove reaction generate thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The mixing of S etc.
Gas).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 92%, and in product, hydrogen and carbon monoxide contains
Amount is 90%, and the ratio of hydrogen and carbon monoxide is 3.6:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 91%.
Embodiment 3
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.06 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-15%FeCl3；Pulverized coal particle is added and stores
In hot type pyrolysis oven, and it is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to 2.5kg:1kg's
Proportioning is in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure storing under conditions of being about 22KPa
In hot type pyrolysis oven, reaction generates thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The gaseous mixture of S etc.).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 87%, and in product, hydrogen and carbon monoxide contains
Amount is 86%, and the ratio of hydrogen and carbon monoxide is 2.7:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 88%.
Embodiment 4
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.08 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-14.5%FeCl3-1.5%Ca (Ac)2；By powder
Coal particle adds in heat storage type pyrolysis stove, and is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to
2.5kg:1kg proportioning in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure be about 22KPa
Under conditions of in heat storage type pyrolysis stove reaction generate thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The mixing of S etc.
Gas).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 93%, and in product, hydrogen and carbon monoxide contains
Amount is 91%, and the ratio of hydrogen and carbon monoxide is 3.4:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 92%.
Embodiment 5
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.06 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-14.5%FeCl3-1.5%Ca (Ac)2；By powder
Coal particle adds in heat storage type pyrolysis stove, and is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to
2.5Kg:1.5kg proportioning in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure be about 22KPa
Under conditions of in heat storage type pyrolysis stove reaction generate thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The mixing of S etc.
Gas).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 93%, and in product, hydrogen and carbon monoxide contains
Amount is 92%, and the ratio of hydrogen and carbon monoxide is 3.9:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 92%.
Comparative example 1
With reference to Fig. 5, fine coal is carried out pressure ball process, obtains the pulverized coal particle of a diameter of 10～50mm；Pulverized coal particle is added
In heat storage type pyrolysis stove, and it is passed through steam and carries out catalytic gasification reaction (not using catalyst), make pulverized coal particle and steam
According to the proportioning of 2.5kg:1kg in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure be about 22KPa
Under conditions of in heat storage type pyrolysis stove reaction generate thick reducing gases (CH4、CO2、CO、H2With a small amount of H2The mixing of S etc.
Gas).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 73%, and in product, hydrogen and carbon monoxide contains
Amount is 75%, and the ratio of hydrogen and carbon monoxide is 2.1:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 78%.
Comparative example 2
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: being that 2.5:0.01 (a small amount of catalyst) is uniform by fine coal and catalyst according to mass ratio mixes also
Carrying out pressure ball process, obtain the pulverized coal particle of a diameter of 10～50mm, catalyst uses
84%K2CO3-14.5%FeCl3-1.5%Ca (Ac)2；Pulverized coal particle is added in heat storage type pyrolysis stove, and be passed through steam and carry out
Catalytic gasification reacts, and makes pulverized coal particle and steam according to the proportioning of 2.5kg:1kg in heat storage type pyrolysis reaction in furnace.Control
Reaction temperature is 650～800 DEG C, pressure is about under conditions of 22KPa reaction in heat storage type pyrolysis stove and generates thick reducing gases
(CH4、CO2、CO、H2With a small amount of H2The gaseous mixture of S etc.).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 80%, and in product, hydrogen and carbon monoxide contains
Amount is 79%, and the ratio of hydrogen and carbon monoxide is 2.5:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 82%.
Comparative example 3
With reference to Fig. 5, the method and system utilizing catalytic coal gasifaction to prepare shaft furnace reducing gases produces the reduction produced needed for sponge iron
Gas technique, its step is as follows: be that 2.5:0.06 uniformly mixes and carries out pressure ball process by fine coal and catalyst according to mass ratio,
Obtaining the pulverized coal particle of a diameter of 10～50mm, catalyst uses 84%K2CO3-14.5%FeCl3-1.5%Ca (Ac)2；By powder
Coal particle adds in heat storage type pyrolysis stove, and is passed through steam and carries out catalytic gasification reaction, make pulverized coal particle and steam according to
The proportioning of 1kg:1kg (in a large number) is in heat storage type pyrolysis reaction in furnace.Control reaction temperature be 650～800 DEG C, pressure is about
Under conditions of 22KPa, in heat storage type pyrolysis stove, reaction generates thick reducing gases (CH4、CO2、CO、H2With a small amount of H2S etc.
Gaseous mixture).
The thick reducing gases of high temperature going out heat storage type pyrolysis stove enters scrubbing tower, the acid of wash tower bottoms after waste heat boiler recovery waste heat
Property water enter catalyst reclaimer, reclaim catalyst；Reducing gases (temperature about 40 DEG C, pressure after the washing of scrubbing tower top
For 22KPa (G)) enter bottom desulfurizing tower top-down MDEA (N methyldiethanol amine) the solution counter current contacting with in tower
Absorb overwhelming majority H2S gas.Go out reducing gases (pressure about 0.02MPa (G), the H of desulfurizing tower2S content is less than 5ppm)
Enter tower top cooler, the reducing gases heated up because of absorption is cooled to about 40 DEG C and carries out gas-liquid separation, reclaim MDEA and absorb
Liquid, reducing gases is cooled and after gas-liquid separation, sends into compressor pressure-raising.(reducing gases pressure about 1.0 after compressor pressure-raising
MPa (G), temperature about 40 DEG C) enter decarbonizing tower and carry out carbon dioxide removal and obtain refined reducing gases.
By the composition in gas chromatographic analysis gaseous product, efficiency of carbon con version is 95%, and in product, hydrogen and carbon monoxide contains
Amount is 91%, and the ratio of hydrogen and carbon monoxide is 4.3:1.Pipe is entered after gas-liquid separation by cooled for above-mentioned refined reducing gases
Formula stove is heated to about 900 DEG C, smelts iron subsequently in shaft furnace, and degree of metalization is 90%.
In the present invention, unless otherwise clearly defined and limited, term " install ", " being connected ", " connection ", the art such as " fixing "
Language should be interpreted broadly, and connects for example, it may be fixing, it is also possible to be to removably connect, or integral；Can be machinery
Connect, it is also possible to be electrical connection；Can be to be joined directly together, it is also possible to be indirectly connected to by intermediary, can be two units
Connection within part or the interaction relationship of two elements.For the ordinary skill in the art, can be according to tool
Body situation understands above-mentioned term concrete meaning in the present invention.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " concrete example ",
Or specific features, structure, material or the feature bag that the description of " some examples " etc. means to combine this embodiment or example describes
It is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term necessarily
It is directed to identical embodiment or example.And, the specific features of description, structure, material or feature can be arbitrary
Individual or multiple embodiment or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be combined by art personnel
And combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is exemplary,
Being not considered as limiting the invention, those of ordinary skill in the art within the scope of the invention can be to above-described embodiment
It is changed, revises, replaces and modification.
Claims (9)
1. the method that a catalytic coal gasifaction prepares shaft furnace reducing gases, it is characterised in that including:
Pressure ball process is carried out with catalyst, in order to obtain pulverized coal particle after being mixed by fine coal；
Make described pulverized coal particle react with steam generation catalytic gasification in heat storage type pyrolysis stove, in order to generate containing hydrogen,
The thick reducing gases of carbon monoxide, carbon dioxide and hydrogen sulfide；
Described thick reducing gases is carried out waste heat recovery, in order to produce steam；
Thick reducing gases through described waste heat recovery is carried out purification processes, in order to obtain refined reducing gases,
Wherein,
In described refined reducing gases, the total content of hydrogen and carbon monoxide is for being not less than 88 volume %, described hydrogen and a described oxygen
The volume ratio changing carbon is (3.5～1.5): 1；The oxidizability of described refined reducing gases is less than 5%；
The reaction of described catalytic gasification is to carry out under the pressure of 650～800 degrees Celsius and 22KPa,
The mass ratio of described fine coal, catalyst and steam is: (1～4): (0.01～0.08): 1.
Method the most according to claim 1, it is characterised in that described catalyst be selected from alkali metal, transition metal,
The oxide of at least one of alkaline-earth metal or salt,
Wherein, described alkali metal is selected from least one of lithium, sodium, potassium, rubidium and cerium；
Described transition metal is at least one of vanadium, chromium, manganese, ferrum, cobalt, nickel, copper and molybdenum；
Described alkaline-earth metal is at least one of magnesium, calcium and barium；
The type of described salt is carbonate, sulfate, heavy carbonate, formates, oxalates, amino-compound, hydroxide
Thing, acetate at least one.
Method the most according to claim 2, it is characterised in that contain the institute of 0.1～3.0 weight % in described catalyst
State oxide and/or the salt of described alkaline-earth metal of alkaline-earth metal.
Method the most according to claim 1, it is characterised in that the described water vapour described waste heat recovery produced returns
React for described catalytic gasification.
Method the most according to claim 1, it is characterised in that described purification processes includes:
Thick reducing gases through described waste heat recovery is carried out carrying out washing treatment, in order to remove the catalysis of residual in described thick reducing gases
Agent and fine ash；
Thick reducing gases through described carrying out washing treatment is carried out desulfurization process, in order to remove hydrogen sulfide gas；
It is compressed the thick reducing gases processed through described desulfurization processing；And
The thick reducing gases processed through described compression is carried out carbonization treatment, in order to remove carbon dioxide and obtain described refined reduction
Gas.
Method the most according to claim 5, it is characterised in that described desulfurization process and carbonization treatment all use N-first
Base diethanolamine is carried out.
7. a catalytic coal gasifaction prepares the system of shaft furnace reducing gases, it is characterised in that including:
Heat storage type pyrolysis stove, described heat storage type pyrolysis stove has fine coal catalyst granules import, water vapour import and thick reducing gases
Outlet, described heat storage type pyrolysis stove is suitable to fine coal, water vapour and occurs catalytic gasification to react under the effect of catalyst, in order to raw
Become containing hydrogen, carbon monoxide, carbon dioxide and the thick reducing gases of hydrogen sulfide；
Waste heat boiler, described waste heat boiler has thermal reduction gas import, the outlet of cold reducing gases and steam (vapor) outlet, described thermal reduction
Gas import is connected with the outlet of described thick reducing gases, and described waste heat boiler is suitable to described thick reducing gases is carried out waste heat recovery, in order to
Produce steam；
Purifying plant, described purifying plant have cold reducing gases import and refined reducing gases outlet, described cold reducing gases import with
The described cold reducing gases outlet of described waste heat boiler is connected, and described purifying plant is suitable to the thick reduction through described waste heat recovery
Gas carries out purification processes, in order to obtain refined reducing gases.
System the most according to claim 7, it is characterised in that the described steam (vapor) outlet of described waste heat boiler and described storage
The described water vapour import of hot type pyrolysis oven is connected, in order to described steam is used for the reaction of described catalytic gasification.
System the most according to claim 7, it is characterised in that it is suitable that described purifying plant farther includes to be sequentially connected
In the described thick reducing gases through described waste heat recovery is carried out carrying out washing treatment, desulfurization process, compression process and carbonization treatment
Washing facility, desulphurization plant, compression device and decarbonation appliance, wherein, described washing facility is connected with described waste heat boiler.
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| CN104538645B (en) * | 2014-12-22 | 2016-09-28 | 山西大学 | Active coke raw powder's production technology for SOFC |
| CN105396574B (en) * | 2015-11-25 | 2017-10-24 | 杨秋良 | A kind of method that Recovery and recycle of compound coal gasification catalyst is utilized |
| CN106076313B (en) * | 2016-06-06 | 2019-01-04 | 湖北华威斯新能源科技有限公司 | The method for preparing vanadium based gas catalyst using vanadium-containing material |
| CN106191362B (en) * | 2016-09-13 | 2018-02-09 | 江苏省冶金设计院有限公司 | A kind of nozzle-type of gas-based shaft kiln also Primordial Qi enters furnace apparatus and its method |
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| ZA78154B (en) * | 1977-01-24 | 1978-12-27 | Exxon Research Engineering Co | System for the recovery of alkali metal compounds for re-use in a catalytic coal conversion process |
| US4193772A (en) * | 1978-06-05 | 1980-03-18 | Exxon Research & Engineering Co. | Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue |
| CN1140746A (en) * | 1995-07-14 | 1997-01-22 | 三田工业株式会社 | Coal gasification apparatus |
| CN1237152C (en) * | 2001-08-08 | 2006-01-18 | 煤炭科学研究总院北京煤化学研究所 | Powdered coal fluidized bed gasification method and gasification furnace |
| CN1288226C (en) * | 2004-04-29 | 2006-12-06 | 福州大学 | Low activity dust coal catalytic gasifying method |
| WO2009111342A2 (en) * | 2008-02-29 | 2009-09-11 | Greatpoint Energy, Inc | Carbonaceous fines recycle |
| EP2370549A1 (en) * | 2008-12-30 | 2011-10-05 | Greatpoint Energy, Inc. | Processes for preparing a catalyzed coal particulate |
| CN102002547A (en) * | 2010-12-09 | 2011-04-06 | 中冶赛迪工程技术股份有限公司 | Gasification furnace gas process for reduction process of coal gasification shaft furnace |
| CN103382401B (en) * | 2012-05-02 | 2015-01-28 | 新奥科技发展有限公司 | Gasification raw material, preparation method of the gasification raw material, and catalytic gasification method adopting the gasification raw material |
| CN103667568B (en) * | 2013-05-23 | 2016-03-30 | 北京神雾环境能源科技集团股份有限公司 | Middle low-rank coal vaporizing system is for reducing gas moving-bed novel process for smelting and system |
| CN203904284U (en) * | 2014-05-14 | 2014-10-29 | 北京神雾环境能源科技集团股份有限公司 | System for preparing reducing gas for shaft furnace through catalysis and gasification of coal |
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