CN1995291B - Method for producing CO cleaning gas catalyzed by carbonate ore and carbon - Google Patents
Method for producing CO cleaning gas catalyzed by carbonate ore and carbon Download PDFInfo
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- CN1995291B CN1995291B CN 200610031110 CN200610031110A CN1995291B CN 1995291 B CN1995291 B CN 1995291B CN 200610031110 CN200610031110 CN 200610031110 CN 200610031110 A CN200610031110 A CN 200610031110A CN 1995291 B CN1995291 B CN 1995291B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000004140 cleaning Methods 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002737 fuel gas Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000002309 gasification Methods 0.000 claims description 23
- 239000003610 charcoal Substances 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001748 carbonate mineral Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 238000009795 derivation Methods 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 2
- 150000005323 carbonate salts Chemical class 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 239000003034 coal gas Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000003245 coal Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000567 combustion gas Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 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 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention discloses a new making method of CO clean fuel gas catalyzed by carbonate salt mineral and carbon, which comprises the following steps: adopting carbonate as raw material; grinding carbon and catalyst; blending; making the reacting material; transmitting into reactor or reacting furnace; insulating air; heating; catalyzing; gasifying; guiding the gasified material; purifying; reserving; liquefying; draining the slag as cement slurry or architectural material or metallurgy and fuel purifier; using residual heat to heat air and raw material.
Description
Technical field:
The present invention relates to energy technology field, being specifically related to carbonate minerals and carbon is that catalytic material is made clean CO gas technology.
Background technology:
Coal gasification is to utilize vaporized chemical to change the organism of coal and destructive distillation product thereof such as semicoke, broken charcoal, coke the process of coal gas into to greatest extent always.Used vaporized chemical is water vapor, air or oxygen, hydrogen, and vaporized chemical is during by red-hot solid fuel layer, the free oxygen wherein or carbon in the fuel is converted into CO, H in conjunction with oxygen such as water vapour or carbonic acid gas or hydrogen
2Or CH
4Gas etc. flammable composition.Certainly other means of producing coal gas by coal also have high temperature carbonization, low-temperature pyrolysis, and the coal gas of destructive distillation gained is called destructive distillation gas, its gas yield far beyond gasification for low.The patent of current domestic and international industrialization gasification process and utilisation technology can be summarized as follows:
1. according to the difference of used vaporized chemical, producer gas is divided into:
1. air gas: the coal gas that generates as vaporized chemical with air.The nitrogen and a certain amount of CO and a spot of CO that wherein contain have an appointment 65% (volume fraction)
2And H
2, the coal gas net calorific value is 3762～4598KJ/m
3
2. mixed gas: the mixture with air and an amount of water vapor is the coal gas that vaporized chemical generates, and the coal gas net calorific value is 5016～6270KJ/m
3
3. water-gas: with the coal gas that water vapor generates as vaporized chemical, the coal gas net calorific value is 10032～11286KJ/m
3
4. semi-water gas: with the water vapor be main an amount of air or the oxygen-rich air of adding simultaneously as the prepared coal gas of vaporized chemical, the coal gas net calorific value is 11704～13376KJ/m
3
5. steam one oxycoal gas: industrial oxygen is infeeded producer gas generator, supply with the prepared coal gas of suitable water vapor simultaneously, the coal gas net calorific value is 10032～10450KJ/m
3
Several industrial gass composed as follows:
2. can be divided into external-heat, internal heat type, thermal barrier formula with heat transfer type.
3. can be divided into moving-bed gasification, ebullated bed gasification, entrained flow gasification, molten bath gasification with the situation of fuel in stove.
Coal gasification technological development direction and up-to-date patented technology are embodied in the following aspects both at home and abroad at present:
1. utilize oxygen to make vaporized chemical.
2. improve gas making pressure, pressure is brought up to 8.0～10.0MPa as the strange 100 type stoves in Shandong.
3. increase stove diameter and volume, improve per unit area yield tolerance.
4. increase feed coal subject range, especially develop fine coal gas making.
Generating is combined, development gas turbine, the generating of steam turbine compound cycle with producing inexpensive low-heat value gas.
6. utilize nuclear energy system gas, enlarge the energy source range, improve the utilization ratio of coal:
7. emthod of high-concentration coal-water slurry (adding dispersion agent) is done raw material, ash group ball deslagging.
8. catalytic gasification: under pressurized gasification medium situation, add catalyzer.
9. radiant heating, the quick coking gasification of fine coal.
Summary of the invention:
Technical problem to be solved by this invention is: solve the problem that above-mentioned prior art exists, and provide a kind of and adopt that the transformation efficiency height of brand new technical route, carbon, coal gas net calorific value are big, manufacturing C0 clean fuel gas method that the energy consumption that economizes on resources, coal gas purify easily.
The technical solution used in the present invention is: carbonate raw material, carbon and catalyzer grinding to 80 μ m are together tailed over＜20%, or the grinding remix is even separately, make reaction material, with powdery or corning or make piece and send into reactor or Reaktionsofen, heatable catalytic gasification reaction under the secluding air condition, adjust gasification reaction temperature and pressure, temperature of reaction in 500 ℃～1100 ℃ scopes, reaction pressure at normal pressure to 5.0MPa, the reaction vapour is derived, and the vapour of derivation stores after purifying treatment is clean CO or liquefies; The mol ratio of above-mentioned carbonate and carbon is 1: 0.5～1.8, promptly by a carbonate CO
3 2-0.5～1.8 carbon atom of proportioning; Described catalyzer is Vanadium Pentoxide in FLAKES and salt of wormwood, perhaps ferric oxide and Repone K, the perhaps violent and cerium dioxide of naphthenic acid; It is as follows that catalyst consumption accounts for the per-cent of carbonate raw material, carbon and total catalyst weight: Vanadium Pentoxide in FLAKES and salt of wormwood sum 1.0%, perhaps ferric oxide and Repone K sum 3.5%, perhaps manganese naphthenate and cerium dioxide sum 1.5%.
The waste residue of discharging partly can be used as the cement raw mix proportioning raw material or makes material of construction or supply metallurgy, and the part waste residue is as gas-purification agent recycle, and waste heat is through heat exchange preheating heat supply air and preheating reaction raw materials.
Above-mentioned under the air-isolation condition heatable catalytic gasification reaction, refer to not add gasifying mediums such as air, steam, hydrogen, former reactor or reaction furnace air are heated and discharge or extract out.
Carbonate in above-mentioned refers to wagnerite (MgCO
3), spathic iron ore (FeCO
3), water chestnut (soft) manganese stone (MnCO
3), rhombspar (CaMg (CO
3)
2), Wingdale (CaCO
3), soda ash (Na
2CO
3) and the compound of other carbon containing acid group in one or more.
Carbon in above-mentioned refers to one or more in coal and destructive distillation product, graphite, charcoal, bamboo charcoal and other vegetation charcoal.Coal carbonization product such as semicoke, broken charcoal, coke.
Catalyzer in above-mentioned refers to potassium, sodium, lithium, caesium, nickel, titanium, platinum, palladium, rhodium, osmium, gallium, iridium, vanadium, tungsten, iron, aluminium, chromium, strontium, zirconium, cobalt, cerium, lanthanum, manganese, copper, the muriate of zinc, bromide, sulfide, vitriol, oxymuriate, vanadate, chromic salt, manganate, titanate, nitrite, nitrate, formate, acetate, salicylate, succinate, Citrate trianion, tartrate, naphthenate, soap, the oil hydrochlorate, carbonate, in phosphoric acid salt and oxide compound and other complex compound one or more.
The invention solves following technical problem is: 1. selection of catalysts, and make " class homogeneous phase " catalyst system; 2. type of heating and reactor (stove); 3. the selection of temperature and pressure and control; 4. explosion-proof; 5. UTILIZATION OF VESIDUAL HEAT IN and waste residue utilization; 6. Bi Yao after measure; 7. purify the storage or the liquefaction of CO combustion gas.
We prove through repetition test for many years: but we produce clean CO combustion gas with carbonate minerals and carbon catalytic gasification, the transformation efficiency of carbon almost can reach 100% in the fuel, and a fuel " C " can produce two " CO ", and one of them CO derives from the carbon in the carbonate.Promptly 1 kilogram of pure carbon " C " can produce 4.66 kilograms " CO " in theory.1 kilogram of " C " 34067KJ of its Lower heat value can produce combustion gas " CO " 47085KJ (1 kilogram of CO Lower heat value 10104KJ), and the combustion gas of generation " CO " calorific value increases about 38.21% than fuel " C is solid " calorific value.
Advantage of the present invention and unusual effect:
1. innovate industry and domestic gas manufacturing technology, adopted the brand-new technology route of " carbonate and charcoal are raw material " reaction.
2. utilize the carbon in the carbonate minerals, and greatly improved the transformation efficiency of fuel " carbon ".The present invention's 1 kilogram of pure carbon in theory can produce 4.66 kilograms of carbon monoxide, and conventional art in theory 1 kilogram of pure carbon all be converted into CO and only can produce 2.33 kilograms of carbon monoxide in theory.Its advantage is expressed as follows with three kinds of oxidation reaction of carbon:
(a)C+O
2＝CO
2+409(KJ/mo?l) 2C+O
2＝2CO+246(KJ/mol)
(b)C+CO
2＝2CO-162(KJ/mol)
(c)2CO+O
2＝2CO
2+571(KJ/mol)
3. adopted functional catalysis technique to reduce reaction activity, the generation of selectivity catalysis CO impels reaction MCO
3+ C=MO+2CO and CO
2+ C=2CO is carrying out than suitable jasmine under the less energy-consumption.
4. made full use of " balance decomposition pressure " characteristic of carbonate minerals, and, promoted MCO by katalysis
3The carrying out of+C → MO+2CO reaction significantly reduced the branch heat of desorption of carbonate minerals, saved energy consumption.
5. utilized waste heat preheating heat supply air and reaction material, further saved energy consumption, and can make full use of waste residue as building materials or metallurgical raw material.
6. coal gas purifies easily, and (as being raw material with Wingdale and coal, waste residue is mainly CaO, adds water CaO+H can to utilize reacted waste residue purification
2O=Ca (OH)
2, vapour is by milk of lime Ca (OH)
2+ CO
2=CaCO
3+ H
2O Ca (OH)
2+ H
2S=CaS+2H
2O), can produce clean high-purity " CO " combustion gas.
Embodiment:
Carbonate raw material, carbon and catalyzer grinding to 80 μ m are together tailed over＜20%; or the grinding remix is even separately; make reaction material; with powdery or corning or make piece and send into reactor or Reaktionsofen; (promptly do not add gasifying mediums such as air, steam, hydrogen at secluding air; air is heated and discharges or extract out in the former reactor) heatable catalytic gasification reaction under the condition, the suitable radiation heating catalytic gasification that adopts of wherein block reaction material.Look raw material and technology controlling and process and require to adjust gasification reaction temperature and pressure (temperature of reaction in 500 ℃～1100 ℃ scopes, reaction pressure preferred to 5.0MPa) at normal pressure.The reaction vapour is derived.The vapour of deriving stores after purifying treatment is clean CO or liquefies.The waste residue of discharging partly can be used as the cement raw mix proportioning raw material or makes material of construction or supply metallurgy, and the part waste residue is as gas-purification agent recycle, and waste heat is through heat exchange preheating heat supply air and preheating reaction raw materials.
Know-why of the present invention is: utilize under certain temperature and pressure condition carbonate and charcoal reaction to generate the CO of CO and carbonate decomposition
2Generate CO with the C reaction, and utilize merit acyl catalyzer to reduce reaction activity, the generation of selectivity catalysis CO.Its main chemical reactions equation is as follows:
MCO
3+C＝MO+2CO………………(1)
MCO
3＝MO+CO
2…………………(2)
CO
2+C＝2CO……………………(3)
M in the reaction formula represents Ca, Mg, Mn, Fe and other metal ion.
Embodiment 1. got wagnerite and coke mol ratio 1: 1, add common grinding to 80 μ m such as gross weight 1.0% catalyzer Vanadium Pentoxide in FLAKES and salt of wormwood and tail over 0.6%, secluding air is gasification reaction under 650 ℃, 0.2MPa air pressure, the reaction vapour is derived, the transformation efficiency 99.99% of fuel carbon, purify back CO content 99.9% with milk of lime, Lower heat value is 12628KJ/m
3
Embodiment 2. gets Wingdale and common grinding to 80 μ m such as hard coal mol ratio 1: 1, interpolation gross weight 3.5% catalyzer ferric oxide and Repone K tail over 0.3%, secluding air is gasification reaction under 900 ℃, normal pressure, the reaction vapour is derived, the transformation efficiency 99.8% of fuel carbon, purifying back coal gas volume ratio with milk of lime is CO 94.3%, H
24.6%, CH
40.7%, H
2S 0.0%, and Lower heat value is 12638KJ/m
3
Embodiment 3. got spathic iron ore and coke mol ratio 1: 1.3, add 1.5% catalyzer manganese naphthenate and cerium dioxide etc., separately grinding to 80 μ m tail over＜2%, mix and be pressed into piece, secluding air is gasification reaction under 850 ℃, 0.4MPa air pressure, vapour is derived, and CO content 99.9%, Lower heat value are 12623KJ/m after purifying with milk of lime
3, waste residue is a sponge iron, degree of metalization 99.3% can be used for steel-making etc.
Claims (2)
1. one kind is the method that raw material is made the CO clean fuel gas with carbonate minerals and carbon, it is characterized in that carbonate raw material, carbon and catalyzer grinding to 80 μ m are together tailed over＜20%, or the grinding remix is even separately, make reaction material, with powdery or corning or make piece and send into reactor or Reaktionsofen, heatable catalytic gasification reaction under the secluding air condition; Adjust gasification reaction temperature and pressure, temperature of reaction in 500 ℃～1100 ℃ scopes, to 5.0MPa, derive by the reaction vapour at normal pressure for reaction pressure, the vapour of derivation stores after purifying treatment is clean CO or liquefies; The mol ratio of above-mentioned carbonate and carbon is 1: 0.5～1.8, promptly by a carbonate CO
3 2-0.5～1.8 carbon atom of proportioning; Described catalyzer is Vanadium Pentoxide in FLAKES and salt of wormwood, perhaps ferric oxide and Repone K, perhaps manganese naphthenate and cerium dioxide; It is as follows that catalyst consumption accounts for the per-cent of carbonate raw material, carbon and total catalyst weight: Vanadium Pentoxide in FLAKES and salt of wormwood sum 1.0%, perhaps ferric oxide and Repone K sum 3.5%, perhaps manganese naphthenate and cerium dioxide sum 1.5%.
2. according to claim 1 is the method that raw material is made the CO clean fuel gas with carbonate minerals and carbon, it is characterized in that described carbon refers to one or more in graphite, charcoal, bamboo charcoal and other vegetation charcoal.
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| CN103881747B (en) * | 2014-04-09 | 2016-01-20 | 山西广通粉末冶金材料有限公司 | Be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas |
| CN103865555B (en) * | 2014-04-09 | 2015-08-26 | 太原理工大学 | A kind of benefit carbon method of dry distillation gas methane synthetic gas |
| CN103881777B (en) * | 2014-04-09 | 2015-11-25 | 太原理工大学 | Be that raw material is through autonomous method of mending carbon production synthetic natural gas with dry distillation gas |
| CN105441135A (en) * | 2014-06-25 | 2016-03-30 | 通用电气公司 | Coal gasification method |
| CN110342770A (en) * | 2019-07-15 | 2019-10-18 | 河南城建学院 | Sludge chemical chain gasification system and technique based on steel slag oxygen carrier |
| CN115403286A (en) * | 2021-05-28 | 2022-11-29 | 中国科学院大连化学物理研究所 | A method of using a solid reducing agent to catalyze the reduction and decomposition of limestone to produce clinker and co-produce CO |
| CN115403282A (en) * | 2021-05-28 | 2022-11-29 | 中国科学院大连化学物理研究所 | A method of using a gas reducing agent to catalyze the reduction and decomposition of limestone to produce clinker and co-produce rich CO/H2 |
| CN116969697A (en) * | 2022-04-21 | 2023-10-31 | 西南科技大学 | A method for producing gas co-production cement from limestone |
| CN114772961B (en) * | 2022-05-05 | 2023-09-19 | 合肥工业大学 | A process for producing cement and carbon monoxide by co-pyrolysis of cement raw meal and solid carbon source |
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