CN101338231A - Natural gas or hydrogen gas made from coal - Google Patents
Natural gas or hydrogen gas made from coal Download PDFInfo
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- CN101338231A CN101338231A CNA2006100751858A CN200610075185A CN101338231A CN 101338231 A CN101338231 A CN 101338231A CN A2006100751858 A CNA2006100751858 A CN A2006100751858A CN 200610075185 A CN200610075185 A CN 200610075185A CN 101338231 A CN101338231 A CN 101338231A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000003245 coal Substances 0.000 title claims abstract description 88
- 239000003345 natural gas Substances 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- 239000001257 hydrogen Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 19
- 230000023556 desulfurization Effects 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 36
- 238000002309 gasification Methods 0.000 claims description 31
- 230000009466 transformation Effects 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 13
- 238000005261 decarburization Methods 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 235000009508 confectionery Nutrition 0.000 claims description 9
- 238000005262 decarbonization Methods 0.000 claims description 9
- 208000005156 Dehydration Diseases 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000009434 installation Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000009272 plasma gasification Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- -1 dedusting Chemical compound 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 238000005243 fluidization Methods 0.000 abstract 2
- 238000004064 recycling Methods 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000010248 power generation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000000844 transformation Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000003209 petroleum derivative Substances 0.000 description 6
- 238000000629 steam reforming Methods 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005200 wet scrubbing Methods 0.000 description 2
- 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 1
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 201000004569 Blindness Diseases 0.000 description 1
- 241000273930 Brevoortia tyrannus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
The present invention discloses a natural gas-like fuel and a method of utilizing coal and other energy substances with an intermediate product hydrogen as the gasifying agent to produce natural gas-like fuel or high-purity hydrogen with methane as the main component. Coal and hydrogen are gasified into similar natural gas in a gasifying device; part or whole of the similar natural gas is reformed with overheat steam produced by the system to obtain hydrogen after fine desulfurization; hydrogen and coal-gasified similar natural gas supply similar natural gas or hydrogen to the system in the recycling process so as to convert the chemical energy of coal and other energy substances into the chemical energy of similar natural gas or hydrogen; the conversion rate of the chemical energy is higher than indirect fluidization and direct fluidization of coal or alcohol ether fuel production. The present invention is a high-efficiency clean coal technology and the similar natural gas can be used for civilian, industrial and commercial use or gas-steam joint recycling power generation and heating.
Description
Technical field:
The present invention relates to the clean coal technology field.
Technical background: China " National Program for Medium-to Long-term Scientific and Technological Development (2006-2020) " energy problem is listed in the top priority of major fields, and wherein gordian technique is a clean coal technology.Coal was broken through 2,000,000,000 tons of high pointes in 2005 as Chinese basic energy resource, and the situation is tense to make Chinese Energy Safety and environment protection, and can the clean coal technology that develop save energy be related to the success or failure of building a resource-conserving and environment-friendly society.Clean coal technology is to make coal should reach the utilization of potential to greatest extent as a kind of energy, and the pollution that discharges is controlled at minimum level, reaches the technology of the efficient clean utilization purpose of coal.The coal utilization technology havoc physical environment that falls behind, in order to make coal high-efficiency, cleaning and convenient the use, must be with gasification of coal or liquefaction.Domestic gas, industrial fuel gas, synthetic gas, coal gas combined cycle generation etc. are produced in gasification of coal.Because the gasification caloric power of gas is low, substitute poor performance with petroleum products, Application Areas exists technology and economic limitation.Coal liquefaction is that petroleum products has direct liquefaction and two kinds of methods of indirect liquefaction at present, liquefaction is converted into coal petroleum products easy to use or produces alcohol-ether fuel, but these schemes all exist technical process length, product composition complexity, processing unit is various, investment is huge, risk is high, transition heat efficient is low, indirect liquefaction thermo-efficiency is about 44%, direct liquefaction is about 58%, and these schemes influence based on traditional petroleum path.In order to improve the thinking of coal energy complete utilization, Syngas park or Poly-generation isotype are proposed, all there are problems such as a large amount of sensible heat utilizations and operational path length in technological process, and the actual energy utilization of large and complete thinking also can not have high-level efficiency.The present invention breaks away from traditional petroleum path and traditional gasification is produced the coal gas thinking, clean coal technology with synthetic class natural gas of coal equal energy source material or hydrogen, coal hydrogenation gasification heat release energy is supplied with the required energy of methane steam reforming, the energy transformation ratio height, can reach more than 80%, product calorific value height, good economy performance, clean fuel easy to use, project investment is less relatively, cost is low, class natural gas is compared with LNG has competitive power, can found the factory and the LNG pipe network is incorporated into the power networks for city, civilian, generating and industrial application coastal.
Because international soaring oil prices, be the China of main energy sources consumption with the coal, almost each has the place of coal large-scale production in the recent period, government and enterprise " the coal system oil " project that all starts in plan, blindness is big, the risk height.Sweet natural gas has substitutability at quite field and petroleum products, even has superiority in field such as civilian than petroleum products.The object of the invention is to develop a kind of fresh fuel-class natural gas of desirable alternative oil and natural gas efficiently, and has features such as less investment, efficient height, cycle weak point.Energy problem is related to safety of China, the clean coal technology project is as national medium-to long-range program for scientific and technological development strategy project, Sweet natural gas and hydrogen are described as the green energy resource of 21st century, with coal system class natural gas or hydrogen is a kind of cleaning with Chinese characteristics, efficient and simple and direct clean coal technology method, can avoid gelatin liquefaction or production alcohol-ether fuel to cause energy serious waste, be the important technology approach of building a resource-conserving society.
Summary of the invention:
The object of the invention be with coal equal energy source material and water synthetic by system's intermediate product hydrogen as vaporized chemical be the high heating value class natural gas or the production High Purity Hydrogen of major ingredient with methane.Tradition gasification product water coal gas because calorific value is low, can not substitute oil and natural gas, and the air separation facility investment is big, energy consumption is high, not high, the total mass flow of system's sensible heat utilization efficient big, purify problems such as insufficient.The liquefaction technology of tradition petroleum path thinking, invest huge, be subjected to international oil price to influence the risk height, energy transformation ratio is low, causes energy serious waste, causes bigger pressure for the exploitation of coal industry, coal in China consumption is increased by a larger margin, against conservation-minded society's requirement.Product type heating value of natural gas of the present invention is suitable with Sweet natural gas, and is good with the alternative performance of petroleum products, can directly be incorporated into the power networks with Sweet natural gas or natural gas liquids pipe network, solves the present natural gas source shortage problem of China.If be used for hydrogen, more traditional coal gas turns to coal gas, through conversion, decarburization, pressure swing adsorption technique thermo-efficiency height, and invests lessly, can be used for synthetic ammonia, refinery shortening or hydrofining etc.
Technical scheme: coal equal energy source material and water synthesize class natural gas or make pure hydrogen as vaporized chemical by intermediate product hydrogen.It is the synthetic gas of major ingredient that coal and hydrogen are converted in gasification installation with methane, through cyclone dust removal, provide heat by heat exchange for the class natural gas steam reformer, it also can be external-heat that class natural gas is reformed, and cooling, udst separation, desulfurization, conversion or methanation, removes carbonic acid gas, removes ammonia, becomes class natural gas.Synthol of the present invention claims class natural gas, and product mainly contains methane and hydrogen, contains a small amount of C
mH
n, CO, CO
2, N
2, H
2Materials such as O, be different from Sweet natural gas (Sweet natural gas does not contain simple substance hydrogen), also be different from the high heating value gas-synthetic natural gas (CO content height) that is rich in methane, combustiblecomponents requires methane content high as far as possible in the class natural gas, 50%～100% scope (molar fraction) for example, hydrogen 0～50%.Carry out steam reformation with the superheated vapour that produces with system after target product class natural gas or pure hydrogen determining section or the further smart desulfurization of all prods, the reformed gas composition mainly contains H
2, H
2O, CO
2, CO, high-temperature gas is used for the hydrogen of gasification and produces steam cooling by heating, through high temperature shift and low temperature shift CO is transformed to CO
2, remove CO
2, H
2Behind the O, with H
2For pressurizeing and be heated to 600 ℃, major ingredient is used for the coal conversion.If with the production High Purity Hydrogen is purpose, then through transformation absorption system High Purity Hydrogen.Coal and hydrogen building-up process heat release energy shortage are with endothermic processes such as steam reformation, production of steam, system radiatings in the system, can contain unconverted incendivity composition semicoke to gasification installation (or reformer) feeding pure oxygen or burning, sulfur-bearing, flue gas only do not need dedusting substantially in the residue, or be that fuel is used to produce endothermic processes such as steam with the synthetic natural gas, or, make system reach energy balance with heating of plasma gasification device or startup.Main chemical reactions:
One, conversion reaction:
C+2H
2→ CH
4(main reaction)
O
2+ 2H
2→ 2H
2O (side reaction)
N
2+3H
2→2NH
3
C+H
2O→CO+H
2
C+O
2→CO
2
CH
4+
1/
2O
2→CO+2H
2
CH
4+H
2O→3H
2+CO
S+H
2→H
2S
Two, methane steam reforming:
CH
4+H
2O→3H
2+CO
ΔH
298K＝206.29KJ/mol
CO+H
2O→CO
2+H
2
ΔH
298K＝-41.19KJ/mol
The perfect combustion reaction:
ΔH
298k＝-879KJ/mol
Partial oxidation reaction:
ΔH
298K＝-36KJ/mol
Generation carbon deposit reaction: 2CO → CO
2+ C
ΔH
298K＝-172.5KJ/mol
CH
4→2H
2+C
ΔH
298K＝74.9KJ/mol
CO+H
2→H
2O+C
ΔH
298K＝-131.47KJ/mol
Water gas shift reaction:
ΔH
298k＝-41.19KJ/mol
Three, methanation
CO+3H
2→CH
4+H
2O ΔH＝-205KJ/mol
CO
2+4H
2→CH
4+2H
2O ΔH＝-165KJ/mol
Overall process:
Scheme can obtain higher energy conversion efficiency.
The coal hydrogenation conversion system can be coal gasification apparatus such as fixed bed, fluidized-bed, air flow bed, melting bed and plasma body.Pressure can be normal pressure or pressurization, as pressure 0～32MPa, the gasification and the invert point scope by conditional decisions such as devices, 800～1500 ℃ on fixed bed, 600～1500 ℃ of fluidized-beds, 800～2500 ℃ of air flow bed.If plasma gasification device thermal plasma temperature can be from thousands of to tens thousand of degree.5000～30000K for example, the cold plasma temperature is lower, for example 100～2000K.Temperature, pressure should from improving total energy efficient and environmental-protecting performance, be optimized processing parameter by the decision of factors such as type of device, coal class, industrial scale.For example in the embodiment of the invention, gasification installation air flow bed pressure 4.5MPa～16MPa, 1400～2200 ℃ of temperature, coal hydrogenation transforms fluidized-bed pressure 4.5～12MPa, 800～1200 ℃ of temperature.Other processing parameters such as desulfurization, conversion, process conditions such as gasification installation pressure are decided about the decarburization equipressure basis, and temperature is determined by selected technology.
Processes such as dedusting in the scheme, desulfurization, conversion and decarburization are as follows:
Dedusting: the present invention uses cyclone dust removal earlier, but one or more levels series connection by electric precipitation, is used wet scrubbing again after lowering the temperature, and wet scrubbing also can combine with sweetening process to be carried out.
Desulfurization: there is differential responses mechanism in different sulfur removal technologies, and the present invention uses the wet method crude desulfurization, and dry desulfurization is smart desulfurization, and wet desulphurization mainly contains chemiadsorption, as alkyl alcoholamine method, alkaline salt solution method etc.; Physisorphtion is as methyl alcohol method, polyethylene glycol dimethyl ether method etc.; The physical-chemical absorption method is as sulfolane process, ordinary temperature methanol process etc.; Wet oxidation process is as improvement ADA method, tannin extract method, ammonia liquor catalysis process, PDS method etc.Dry desulfurization mainly contains: hydrogenation conversion catalyst----iron molybdenum, nickel molybdenum, cobalt molybdenum, nickel cobalt molybdenum etc.; Absorption-type or inversion absorption type----zinc oxide, ferric oxide, manganese oxide etc.; Adsorptive type-----gac, molecular sieve etc.
Conversion: high temperature shift and low temperature shift, high temperature shift temperature range be at 370～485 ℃, available iron chromium-based catalysts, pressure can normal pressure to high pressure 0～32Mpa, operation before and after depending on.The low temperature shift temperature range is at 230～250 ℃, available copper zinc chrome system or Cu-Zn-Al catalyzer, pressure can be from the normal pressure to the high pressure 0～32MPa, operation before and after depending on.
Decarburization: decarbonization process is divided into solvent adsorption method and transformation adsorption method of separation, adopts low-temp methanol method or activation MDEA method, and is capable of reducing energy consumption.
Methanation: 280～420 ℃ of temperature ranges, under catalyst action, make carbon monoxide, carbonic acid gas and hydrogen reaction in the synthetic gas generate methane and water, pressure range can be from the normal pressure to 98MPa, operation before and after depending on.
The coal operation: the coal operation can be used CO
2Or N
2Deng the rare gas element pressurising, mesolow can be used CO
2, high pressure can be used N
2, also available hydrogen pressurising.
Steam reformer can be the partial oxidation steam reformation, can be heat exchange type or locate hot type, and 300～1200 ℃ of temperature ranges, better 600～950 ℃, pressure 0～32Mpa, better 1.6～6.5MPa, catalyzer can be Ni, Pt etc.Other operation desulfurization, conversion, decarburization are decided according to system's coal hydrogenation conversion and steam reformation pressure, and temperature range is decided by selected technology.
If the production high-purity hydrogen can be selected raw hydrogen for use transformation absorption or the pure hydrogen of membrane separation process system.
Technique effect: the present invention coal equal energy source material system class natural gas or hydrogen, make the chemical energy of coal be converted into class natural gas or hydrogen energy to greatest extent, the lime-ash of discharging can be made the lime-ash goods, and desulfurization can be produced sulphur, and extremely goods, decarburization can be produced the discharging of dry ice minimizing room temperature air.It is precious that this technical scheme makes the coal whole body, and energy transformation ratio is much higher than the direct liquefaction and the indirect liquefaction of coal, or produces alcohol-ether fuel, synthetic class natural gas, and alternative class natural gas or LNG are expected to solve the not enough problem of present Chinese natural air-air source.Process for making hydrogen can be used for industries such as oil refining, nitrogenous fertilizer, also can be used for fields such as fuel cell.We can say the present invention be a kind of efficiently, clean clean coal technology with Chinese characteristics.
Description of drawings
Fig. 1. principle of the invention figure, 1 coal hydrogenation conversion system, 2 interchanger, 3 cleaning apparatuss, 4 desulfurizers, 5 class natural gas, 6 smart desulfurization, 7 steam reformers, 8 changing device, 9 take off charcoal, absorption of 10 transformations or membrane sepn.
Fig. 2. a kind of process principle figure of the present invention.
Fig. 3, embodiment of the present invention schema.The synthetic class natural gas device of this scheme coal hydrogenation gasification is a fluidized-bed.The semicoke that gasification produces is used for the hydrogen of gasification with the boiler heating and produces steam being used for vapour reforming hydrogen producing and steam turbine acting.Reformer adopts external-heat, available boiler high temperature flue gas heating, or directly heat at reformer coal combustion oil gas etc., can extract the hydrocracking that hydrogen be used for coal with transformation absorption or membrane sepn when synthetic class natural gas hydrogen content is high.The explanation of figure numbering:
1 fluidized bed coal hydrogasification device, 2 cyclonic separators, 3 coal hydrogenation gas jets, can assist plasma apparatus, 4 boilers, 5 heating-type steam reformers, 6 changing device, 7 cleaning apparatuss, 8 refrigerating units, 9 changing device, 10 decarbonization devices, 11 desulfurizers, 12 smart desulfurizers, 13 changing device, 14 decarbonization devices, 15 dehydrations, absorption of 16 transformations or membrane separation unit, 17 product class natural gas, 18 internal combustion turbine, 19 waste heat boilers, 20 steam turbine, 21 turbocompressors, 22 generators, 23 urban pipe networks or main gas line network.
Fig. 4. the embodiment of the present invention schema.This scheme coal hydrogenation gasification carries out in air flow bed, produces high-temperature synthesis gas, provides energy to vapour reforming hydrogen producing, and synthetic gas and reformed gas heat CH through the pressurization interchanger
4+ H
2O gas mixture and be used for the hydrogen that coal hydrogenation transforms, and produce the high, medium and low voltage steam and be used for steam turbine and provide power for hydrogen compression and class natural gas compression, the pressure superheated vapo(u)r is used for steam reforming in the part.Synthetic class natural gas is used for internal combustion turbine to be provided fuel or is used for urban pipe network etc.For adapting to internal combustion turbine peaking operation mode, scheme is considered high pressure gas bundle or liquefying plant.Number description:
1 pulverized coal preparation system, 2 fine coal storehouses, 3 fine coal lock hoppers, 4 air flow bed coal hydrogenation gasification devices, 5 heat exchange type steam reforming devices, 6 interchanger, 7 low-pressure drums are pressed drum, 9 high pressure drums in 8,10 cleaning apparatuss, 11 desulfurizers, 12 changing device, 13 decarbonization devices, 14 smart desulfurizers, 15 dehydrations, absorption of 16 transformations or membrane separation unit, 17 product class natural gas, 18 changing device, 19 water coolers, 20 decarbonization devices, 21 dehydrations, 22 internal combustion turbine, 23 waste heat boilers, 24 steam turbine, 25 generators, 26 urban pipe networks or main gas line network, 27 high pressure gas bundle or liquefying plants.
Fig. 5. the embodiment of the present invention schema, this scheme enters heat exchange type steam reforming device with the fluidized bed coal hydrogasification through cyclone dust removal (can be multistage) energy is provided, and synthetic gas and reformed gas heat CH by interchanger
4+ H
2O and the hydrogen that is used for coal hydrogenation, and produce high, medium and low voltage superheated vapo(u)r driving turbine for hydrogen compression, transformation absorption or membrane sepn air separation facility, class natural gas compresses or liquefaction provides power.The part superheated vapour is used for the class natural gas steam reformation hydrogen production, is provided as in the scheme to make coal and the well-mixed riser arrangement of hydrogen, is coal, the hydrogen plasma supplementary unit that starts or heat, or to schemes such as deslagging aerating oxygen burning semicokes.Number description:
1 fluidized bed coal hydrogasification device, 2 riser tubes, 3 nozzles, the plasma body supplementary unit, 4 compressors, absorption of 5 transformations or membrane sepn air separation facility, 6 cyclonic separators, 7 heat exchange type steam reforming devices, 8 interchanger, 9 low-pressure drums are pressed drum, 11 high pressure drums in 10,12 cleaning apparatuss, 13 desulfurizers, 14 changing device, 15 decarbonization devices, 16 smart desulfurizers, 17 dehydrations, absorption of 18 transformations or membrane separation unit, 19 product class natural gas, 20 turbocompressors, 21 steam turbines, 22 compressors, 23 changing device, 24 water coolers, 25 desulfurization, 26 dehydrations, 27 high pressure gas bundle or liquefying plants, 28 internal combustion turbine, 29 waste heat boilers, 30 steam turbine, 31 generators, 32 urban pipe networks or main gas line network.
Fig. 6. the embodiment of the present invention schema, this invention, enters the heat exchange type steam reformer energy is provided through the multistage cyclone dedusting with the fluidized bed coal hydrogasification, and the synthetic gas that reformer comes out adds hydrogen and CH at interchanger
4+ H
2The O gas mixture, synthetic gas becomes class natural gas through technologies such as dedusting, desulfurization, and reformed gas is through technology hydrogens such as conversion, decarburizations, through transformation absorption or membrane sepn system High Purity Hydrogen.This scheme can be used for making pure hydrogen or class natural gas.Number description:
1 fluidized bed coal hydrogasification device, 2 cyclonic separators, 3 coal bunkers, 4 compressors, absorption of 5 transformations or membrane separation unit, 6 heat exchange type reformers, 7 interchanger, 8 low-pressure drums are pressed drum in 9,10 high pressure drums, 11 cleaning apparatuss, 12 decarbonization devices, 13 compressors, 14 turbines, 15 compressors, 16 interchanger, 17 conversion, 18 smart desulfurization, 19 decarburizations, 20 height, low temperature shift, 21 interchanger, 22 decarburizations, 23 dehydrations, absorption of 24 transformations or membrane sepn, 25 class natural gas, 26 high pressure gas bundle or liquefying plants, the circulation of 27 gas-steam combined, 28 urban pipe networks or gas line network, 29 device for producing hydrogen.
Embodiment:
| Class natural gas | 96 |
The coal hydrogenation device | Fluidized-bed |
| Calorific value | 38.78MJ/Nm 3 | Gasification temperature | 950℃ |
| Gas production rate | 6.8×10 4m 3/h | Vapor pressure | 8.5MPa |
| Energy transformation ratio | 80％ | Heat exchange type reformation pressure | 4.5MPa |
| Coal consumption ce | 112.1t/h | The heat exchange type reforming temperature | 800℃ |
Device context: apparatus of the present invention mainly contain coal hydrogenation fluidized-bed gasification device, comprise logical oxygen combustionresidue device, heat exchange type steam reformer, interchanger, be used to add hot hydrogen and produce devices such as water vapor device, synthetic gas dedusting, desulfurization, conversion, decarburization, dehydration, class natural gas storage, reformation gasification high and low temperature shift, decarbonization device.
| Class natural gas | 60％CH 4 35％H 2 | The coal hydrogenation gasification device | Air flow bed (shell or Texaco) |
| Calorific value | 28.36MJ/Nm 3 | Gasification temperature | 1700℃ |
| Gas production rate | 3.12×10 4m 3/h | Vapor pressure | 2.5MPa |
| Energy transformation ratio | 70％ | External-heat steam reformation pressure | 4.0MPa |
| Coal consumption ce | 43.2t/h | External-heat steam reformation temperature | 850℃ |
Device context: the broken and feeding device of coal dust, hydrogen turbine compressor, Sweet natural gas steam turbine compressor (being used for the air storage of high pressure gas bundle), system high purity oxygen pressure-swing absorption apparatus, desulfurizer etc.
| Class natural gas | 96 |
The coal hydrogenation gasification device | Fluidized-bed (plasma body supplementary unit) |
| Calorific value | 38.78MJ/Nm 3 | Gasification temperature | 950℃ |
| Gas production rate | 1.29×10 5m 3/h | Vapor pressure | 12MPa |
| Energy transformation ratio | 85％ | Heat exchange type steam reformation pressure | 6.5MPa |
| Coal consumption ce | 200.74t/h | Heat exchange type steam reformation temperature | 900℃ |
The pure hydrogen of embodiment 4. systems adopts Figure of description 6 technologies.
| Hydrogen | 99.9％ | The coal hydrogenation gasification device | Fluidized-bed (plasma body supplementary unit) |
| Calorific value | 12.75MJ/Nm 3 | Gasification temperature | 900℃ |
| Gas production rate | 1.93×10 5m 3/h | Vapor pressure | 6.5MPa |
| Energy transformation ratio | 80％ | Heat exchange type steam reformation pressure | 4.5MPa |
| Coal consumption ce | 100t/h | Heat exchange type steam reformation temperature | 850℃ |
Claims (8)
1. with the synthetic a kind of class natural gas fuel of coal equal energy source material, it is characterized in that the product of coal and hydrogen-gasified, mainly form CH by methane and hydrogen
4Content 50～100%, hydrogen 0～50% contains a small amount of C
mH
n, CO
2, H
2O, N
2, material such as CO, Sweet natural gas does not contain simple substance hydrogen, the difference Sweet natural gas claims class natural gas, also is different from the synthetic natural gas that is rich in the methane high heating value gas.
2. the method for coal equal energy source material system class natural gas or pure hydrogen is characterized in that:
(1) coal equal energy source material and hydrogen are gasificated into the synthetic gas that is rich in methane at gasification installation, and synthetic gas is through system class natural gas such as dedusting, desulfurization, conversion, decarburization, dehydrations;
(2) the part class natural gas is through smart desulfurization, steam reformation or partial oxidation steam reformation, and reformed gas produces raw hydrogen through conversion, decarburization, absorption of hydrogen transformation or membrane sepn system High Purity Hydrogen;
(3) raw hydrogen and coal equal energy source gasification substance system class natural gas; By above-mentioned, the working cycle that goes round and begins again just can outwards provide class natural gas or pure hydrogen.
3. the method for right 2 coal equal energy source material system class natural gas or pure hydrogen, feature are that coal equal energy source material is coal and goods, oil and goods thereof (as refinery coke, residual oil), biomass energy.
4. implement the device of right 2, it is characterized in that coal hydrogenation gasification device, steam reformer, ash handling equipment, desulfurizer, changing device, decarbonization device, transformation absorption or membrane separation unit, plasma gasification installation, high pressure gas bundle or liquefying plant etc.
5. right 4 is implemented the device of rights 2, it is characterized in that the coal hydrogenation gasification device can be devices such as fixed bed, fluidized-bed, air flow bed, melting bed and plasma body, can be that one or more patterns comprise parallel connection or plural serial stage.
6. right 4 is implemented the device of right 2.It is characterized in that steam reformation is steam reformation or partial oxidation steam reformation.
7. right 4 is implemented right 2 devices, it is characterized in that steam system can adopt multistage steam pressure such as a pressure, two pressures, three pressures.
8. right 4 is implemented the device of right 2, it is characterized in that steam reformer is external-heat or heat exchange type.
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| CNA2006100751858A CN101338231A (en) | 2006-05-03 | 2006-05-03 | Natural gas or hydrogen gas made from coal |
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|---|---|---|---|
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