CN104032059B

CN104032059B - Hydrogen metallurgy method

Info

Publication number: CN104032059B
Application number: CN201410305703.5A
Authority: CN
Inventors: 樊显理
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-09-23
Filing date: 2008-09-23
Publication date: 2015-11-18
Anticipated expiration: 2028-09-23
Also published as: CN101768651A; CN104032059A

Abstract

A kind of hydrogen metallurgy method and relevant device, relate to the double hydrogen energy source technical field of hydrogen metallurgy.With pre-reducing furnace to the quick prereduction under rich hydrogen, high temperature, condition of high voltage of iron ore concentrate pellet, produce the sponge iron of reduction degree >=75%, flow to pyrolyzer to be incubated air-tight manner; The combustion gas of gas class through direct current plasma electric arc, is cracked into high temperature hydrogen and nanometer by pyrolyzer under high temperature condition, and most of high temperature hydrogen exports pre-reducing furnace to, and sponge iron is through Flashmelt reduction smelting molten iron discharging or half steel; Utilize the using waste heat from tail gas of pre-reducing furnace simultaneously, produce high-temperature steam, obtain the pure hydrogen of high temperature through water vapour electrolytic tank electrolysis again, the pure hydrogen of high temperature is separated wherein after moisture content through heat exchange, then feeds back to pre-reducing furnace, and wherein part directly exports as hydrogen energy source.Efficient, energy-conservation, best quality product, the best emission reduction effect of hydrogen metallurgy are fully demonstrated.

Description

Hydrogen metallurgy method

Technical field

The present invention relates to metallurgy and energy field.In particular to: the direct current plasma arc high temperature By Direct Pyrolysis hydrogen manufacturing of the perhydrous coal such as hydrocarbon fuel gas, brown coal such as Sweet natural gas, coal-seam gas, underground gas maked coal, shale gas, combustible ice and plant drymeal; The hydrogen manufacturing of metallurgical waste heat high temperature electrolysis of steam; Sponge iron is produced in rich hydrogen reduction; Sponge iron melting goes back original production molten iron or half steel eventually; And its carbonic acid gas, sulfurous gas, discharged nitrous oxides all level off to zero, and high energy saving; Also exportable hydrogen energy supplied automobile hydrogen energy source.

Background technology

1, the metallurgical background technology of hydrogen

Huge blast furnace ironmaking is still the metallurgical ironmaking technology of current main-stream, and this technology is very ripe, output is huge, production cost has much competitive power.But flow process is complicated, investment cost is huge, ton iron more than total energy consumption 18GJ (700kg standard coal), world's coking coal resource and iron high-quality lump ore resource increasingly deficient, production cost increases day by day, compared with hydrogen metallurgical technology of the present invention, too high (the ton iron total energy consumption≤12GJ of the present invention of energy consumption, namely≤400kg standard coal), the Carbon emission of in addition huge blast furnace ironmaking ton iron more than 2.5 tons, it is earth atmosphere environment major source of pollutant, along with global warming threatens the problem of human survival condition to become increasingly conspicuous, blast furnace ironmaking certainly will become the target of everyone, and changing has been inevitable.

COREX coal melting and reducing, is the representative of current emerging metallurgical ironmaking technology, also can have produced iron without coke, but facts have proved that its total energy consumption, carbon emission, production cost three norms all exceed huge blast furnace ironmaking.

Itmk3 rotary hearth furnace high temperature fast restore adds electric arc furnace ironmaking technology, without coke, efficiency also very high, just can produce granulated iron in 10 minutes, within one hour, just can produce molten iron, have the title of third generation in the world ironmaking technology.But extensive industrialization has certain difficulty, to reach the scale of annual output 2000000 tons of molten iron, huge rotary hearth furnace more than 10 seat of diameter 60 meters need be built, also to maintain the different sections of its annular body of heater more than 1300 DEG C high temperature, but reality can only process the mineral aggregate layer of 30 ~ 60 mm thick, area of dissipation is excessive, thermo-efficiency is too low, maintain normal operation and acquire a certain degree of difficulty, and great amount of carbon dioxide emission problem still exists.

Iron ore concentrate superfine powder fast reduction in low temperature adds electric furnace ironmaking technology, is current up-to-date metallurgical technology, will be also minimum in above-mentioned all metallurgical technologies without coke, efficiency also high, energy consumption, oxysulfide, discharged nitrous oxides.And along with continually developing of whole world high-grad iron ore deposit, poor iron ore output proportion is more and more large, fine grinding is selected becomes rich fine iron breeze in pulverizing of will having to, and this is with regard to for providing biggest market for the development of iron ore concentrate superfine powder fast reduction in low temperature.But the discharge of the great amount of carbon dioxide of this iron smelting method is still its root problem; And selected for fine grinding fine iron breeze and the mixing profit further such as coal dust, catalyzer, sweetening agent are worn into as granularity is that 0.04mm accounts for 90% of total powder amount, and mixed pelletizing, manufacture difficulty is higher, and workman's working conditions is poor, also significantly can increase product cost.

2, hydrogen energy source background technology: do not have the cheap energy, just can not carry out hydrogen metallurgy, also can not realize automobile, tractor, steamer, aircraft and mankind's basic living hydrogen energy source.Solve global greenhouse effect, reverse global warming trend, can only be just only a kind of ideal, public opinion, argue, shift responsibility onto others and remote future.

But our times is metallurgical, petrochemical industry, the communications and transportation, domestic fuel etc. such as thermal power generation and automobile, aircraft, boats and ships, every year hundreds billion of tons of oil, Sweet natural gas, coal-seam gas, coal, plant stem body, biogas, acetylene etc. are finally become carbonic acid gas to be completely discharged in air, accumulate over a long period, the basic life condition of the serious threat mankind, this is undisputable fact, the mankind will address this problem, very urgent, but this only has could really be dealt with problems by hydrogen energy source, and there is no alternative at all.

Countries in the world for a long time, are devoted to from hydrogen energy source vehicle starting, develop " hydrogen energy source " and " hydrogen economy ", realize " carbon dioxide discharge-reduction "; Ge great automobile making businessman has also dropped into huge fund and technical force, and national governments also pay much attention to, and has done substantial contribution support; And promoted the main themes become when national governments head converges; Even define the Kyoto Protocol with certain restraint force, however in the whole world general production and supply hydrogen energy source, set up the hydrogenation stations that spreads all over the world, etc. the reality of aspect be effectively in progress but very limited, can be described as and be difficult to starting.Because the automobile distribution whole world will travel in the whole world, any country of any enterprise does not all also have this ability ignore economic benefit and it " can be accomplished in one move ".

Someone proposes, many countries are also spending huge sums research performation " carbonic acid gas landfill ", the carbonic acid gas produced due to the deepwater transportation means of sky cannot collect landfill at all, and this is one does not simultaneously have the unaffordable huge input of economic return enterprise, is more difficult to cash.

Single angle from hydrogen manufacturing, gas water vapour reforming hydrogen producing, is domestic and international petrochemical industry, synthetic ammonia fertilizer industry, methanol industry, metallurgical sponge iron industrial application is maximum, cost is minimum, technically the most ripe fossil fuel hydrogen producing technology; But from the angle reduced discharging, its fundamental drawback often transforms 1 ton of Sweet natural gas, will discharge 4 tons of carbonic acid gas in air.Earth atmosphere environment is difficult to bear really.

Alkaline electrolytic bath water electrolysis hydrogen production does not discharge carbonic acid gas, technically the most ripe hydrogen producing technology at present, and application surface is also comparatively wide, but needs consumption 4.5 ~ 5.5kw.h electric power owing to often making 1 cubic metre of hydrogen, causes energy consumption and high cost.And if with fossil fuel generating electric power is provided, then in fact Carbon emission does not reduce.

Plasma cracking hydrocarbon fuel gas and coal hydrogen manufacturing, acetylene processed is the development of our times various countries hydrogen energy source, hydrogen economy, hydrogen energy source automobile, natural gasification, work Coal Chemical Industry etc., the focus researched and developed.The patent applications such as No. 02128420.2, No. 200310104055.9, No. 200410012523.4 just propose the method and apparatus utilizing plasma pyrolysis hydro carbons and coal to produce carbon black and hydrogen.And inspect analytical proof when hydrocarbon cracking combustion gas through transmission electron microscope and can obtain the nanometer carbon black of 99% pure hydrogen and 5 ~ 50 nanometers.But in existing various practical plasma apparatus, the core technology of its plasma generator is all plasma gun.But to be applied to ironmaking and hydrogen energy source production, then also there is following weak point: (1) is that power is too little, current world's success commercial application ion unit peak power is 2.8 megawatts, maximum operating currenbt 10kA, and alternatively the plasma metallurgy stove of blast furnace ironmaking should at 100 megawatts, more than 100kA, (2) be the negative electrode of plasma gun of existing smelting apparatus, all adopt water-cooled tungsten, niobium, tantalum, molybdenum, hafnium, zirconium, Deng adding thorium in refractory metal, cerium, yttrium, the oxide compound manufacture of ytterbium etc., facts have proved when working current is more than 4kA, this cathode burning corrosion is very serious, and its water cooling plasma gun body directly gos deep into huge and is full of in the metallurgical plasma heating furnace burner hearth core area of hydrogen of High Temperature High Pressure hydrogen, be difficult to resist plasma heating furnace high temperature for a long time in fact, the serious accident that easy generation cannot be retrieved, plasma gun or plasma gun negative electrode is frequently changed to guarantee safety if take, also be unpractiaca, known according to putting into practice of huge blast furnace, the huge blowing out being full of the inflammable and explosive reducing gas of High Temperature High Pressure, be one very complicated, dangerous, cost, consuming time, greatly reduce the work of production efficiency.

In order to solve these significant problems in the metallurgical hydrogen energy source production of hydrogen, the present inventor, once by No. 200610106689.1 patent applications, take the lead in proposing a whole set of " natural gas hydro-cracking metallurgical method and equipment " invention in world's metallurgical technology.After the relevant ferrous metallurgy authoritative expert of Circular of the State Council examines, be confirmed to be a practicable technology with security properties.

But our Science Explorations does not stop, the present invention just represents our new achievement in research, but does not negate last patent application, but it continues great practical innovation and development.

The present inventor assert: world steel industry is the rich and influential family that the rich and influential family of world energy sources centralized consumption and carbonic acid gas concentrate discharge, its energy expenditure and carbonic acid gas actual emission all account for about 20% of world energy sources total quantity consumed and Carbon emission total amount, and its heat utilization rate is less than 40%, its a large amount of high temperature height enthalpy tail gas (heat energy that its heat energy is enough to produce with large-scale nuclear power station compares favourably) is usually directly emptying, only have the advanced smelter of minority just to use it for cogeneration, but its overall thermal efficiency still only have about 50% usually.According to the plasma high temperature By Direct Pyrolysis hydrogen manufacturing of the perhydrous coal such as the Sweet natural gas in the present invention, coal-seam gas, underground gas maked coal, brown coal, " high-temperature vapor water energy wind energy electric power electrolytic hydrogen production " (heat utilization rate that can double than cogeneration), the associating hydrogen production process hydrogen manufacturing combined; And first obtained hydrogen is directly used in metallurgy, and need not long-distance transportation on a large scale, also without the need to first setting up the hydrogenation stations spread all over the world, any country, any large-scale metallurgical enterprise can implement, and can start to walk, and implement all lucrative.Particularly abnormal abundant as China, Russia, Brazil, the U.S., Canada, India, South Africa, Indonesia, Egyptian like this some water energy, wind energy potential, the country that iron and steel production capacity exception is huge, is well worth doing especially.Enjoy once set up low cost forever, free from environmental pollution, do not affect existing defeated power supply plan.Catch this major part of metallurgical carbon dioxide discharge-reduction, containment earth atmosphere warms and gets instant result, hydrogen energy source, hydrogen economy will be shaped day by day, on this basis, progressively hydrogen more than needed for its high-efficiency low energy consumption cheapness is exported the local automobile hydrogen energy source of supply, smelter or vehicle user and human society all lucrative.Thus find a breach from metallurgical industry for the hydrogen energy source hydrogen Economic development in the world.From then on hydrogen energy source, hydrogen economy, will be no longer talk about stratagems on paper, but solidly can spread over a whole area from one point and be progressively developed.

Contriver thinks: " human society is only very high from concentration degree, scale is huge especially ferrous metallurgical industry starts hydrogen energy source process; as breach; reduce discharging concerning the hydrogen energy source of human survival and development, hydrogen economy, global carbon dioxide, just likely rake in substantive breakthroughs and be in progress, the trend that terrestrial climate warms could be contained quickly and effectively ".

Summary of the invention

Object of the present invention outwardly, be to provide a kind of hydrogen metallurgy method, but be actually the hydrogen energy source production method containing ultra-large (ultra-large production can not be realized, just can not replace huge coke blast furnace ironmaking), and hydrogen metallurgy production method two contents; Fully demonstrate: the high-level efficiency of hydrogen metallurgy, less energy-consumption, best quality product, best emission reduction effect (carbonic acid gas, sulfurous gas, oxynitride, all will reduce discharging more than 80% until level off to zero), minimum investment in fixed assets and development investment.And will become as world car, aircraft, steamer hydrogen energy source, the breach of development hydrogen economy.

Another object of the present invention is to provide the specific equipment of hydrogen metallurgy method.Be ensure ultra-large hydrogen energy source production method and the realization of hydrogen metallurgy production method with material conditions and technological measure, do not have theory to be become actual equipment, all can only be all empty talks.Had and the theory of whole hydrogen energy source production method and hydrogen metallurgy production method can have been tried out and the equipment regulated and controled, then Energy production and hydrogen metallurgical production just will become a reality.There is no a unconquerable scientific and technological production difficult problem therebetween, do not had the Great Wall every.And, the hydrogen energy source production unit that the present invention releases and hydrogen metallurgical production equipment, be by hydrogen energy source to produce and hydrogen metallurgical production is combined closely, depended on each other for existence, interwoveness, even to permeate stove, flow process is short, efficiency is high, energy consumption is low and improve its reliability as possible, the ability of running continuously year in year out and ultra-large throughput are metallurgical equipment and the metallurgical technologies that our times uniquely can replace the efficient high product quality of clean energy-saving of blast furnace ironmaking; And this equipment of the present invention can realize the metallurgical ultra-large production of hydrogen, and operates continuously reliably and with long-term, has the high productive capacity and lower production cost of competing mutually with blast furnace ironmaking.

The object of the present invention is achieved like this:

One, the present invention's it " hydrogen metallurgical " is building on following 6 irrefutable the principless of science:

1, Fe ₂o ₃+ 3H ₂→ 2Fe+3H ₂o, namely obtain metallic iron with hydrogen reduction iron oxide ore, its discharge is water vapour, and Carbon emission levels off to zero.Here it is " hydrogen is metallurgical ".Solve unique way that ferrous metallurgy does not discharge carbonic acid gas, not without his way.

2, CH ₄→ 2H ₂+ C: namely for methane plasma Pintsch process hydrogen manufacturing.Cracking 1 mole of methane, directly can obtain 2 moles of pure hydrogen, also can obtain the nanometer carbon black that 1 mole may be used for manufacturing carbon fiber and tire, and Carbon emission levels off to zero.In fact, methane dosage is that accurate calculation is determined in the present invention usually, and participation melting and reducing is entered the pig iron, and do not have the attached product of carbon black by the carbon black that cracking produces; Only when considering from economic benefit, recognize necessary, when also having an economic investment development ability, just in a planned way By-product carbon black; Or only when the restriction owing to being subject to enforcement ground condition, as cleaned renewable cheap water power wind-powered electricity generation nuclear power scarcity of resources, natural gas source is abundant especially, just has to the proportioning of Sweet natural gas to be increased to molten iron 170 ~ 250m per ton ³and By-product carbon black.By-product carbon black, that the one of hydrogen metallurgical production normally extends, have to compared with the extra energy-saving, emission-reducing, environment friendly measure that increases with carbonic acid gas landfill etc., not only simple, but also economical, be again desirable energy-saving, emission-reducing, environment friendly measure only concerning Sweet natural gas, coal-seam gas, shale gas, the resourceful enterprise of underground gas maked coal.

Above two, just establish the basis that the present invention's " hydrogen metallurgical technology " is sure of success.

But our research practice experience of nearly 20 years, knows very well before combustible ice obtains industrialized developing, Sweet natural gas is also a well sold and in short supply and energy for preciousness.Want in a large number for ironmaking, all some feels difficult for everybody.Thus the present invention, add the combination producing technology that following 5 same irrefutable hydrogen manufacturing principles and hydrogen energy source and hydrogen metallurgy are combined closely, the hydrocarbon fuel gas consumption such as Sweet natural gas are reduced to below 100 cubic metres of/ton of iron until be zero, and total energy consumption still can≤12GJ.And " simple natural gas hydro-cracking is metallurgical " is guided into " coal-seam gas or in-situ coal gasification gas conditionally, the multiple hydrocarbon fuel gas cracking such as shale gas is with metallurgical ", " metallurgical waste heat less energy-consumption high-temperature water vapour electrolytic hydrogen is metallurgical ", " hydrocarbon fuel gas cracking hydrogen production combines hydrogen manufacturing with metallurgical waste heat high-temperature water vapour electrolytic metallurgical ", " it is metallurgical that the perhydrous coal+hydrogen such as brown coal or hydrocarbon fuel gas make carrier gas cracking hydrogen ", " it is metallurgical that plant drymeal+hydrogen or hydrocarbon fuel gas make carrier gas cracking hydrogen ", this just makes where district in office, hydrogen energy source and the metallurgical combination producing of hydrogen can be implemented according to the condition of oneself, particularly guide " peak and low valley electric power and metallurgical waste heat less energy-consumption high-temperature water vapour electrolytic hydrogen metallurgical " into and namely " utilize the renewable waterpower wind power station in the world, big vast phase in rainy season, monsoon phase, night, cheap electric power that Holidays, peak and low valley wasted usually, combine with utilizing huge metallurgy high temperature height enthalpy tail gas, extensive hydrogen energy source produces the world's hydrogen path to economic development combined with extensive hydrogen metallurgical production ".

3, C _nh _m→ nC+ (m/2) H ₂, i.e. the plasma high temperature cracking hydrogen production of the multiple hydrocarbon fuel gas such as coal-seam gas or in-situ coal gasification gas, shale gas, petroleum gas, biogas, combustible ice gasification gas.These hydrocarbon fuel gas all successfully can be cracked into hydrogen by the hydrogen smelting pyrolyzer released in the present invention and carbon black smelts molten iron discharging simultaneously;

4, " hydrogen manufacturing of metallurgical waste heat high temperature electrolysis of steam ":

That is: 2H ₂o → 2H ₂+ O ₂, or 2H ₂o → 4H ⁺+ 4e+O ₂, 4H ⁺+ 4e → 2H ₂,

Through lot of experiments, we find in the hydrogen manufacturing of hydrocarbon plasma pyrolysis and hydrogen high temperature fast restore process, produce a large amount of more than 1100 DEG C high-temperature tail gas.Due to the huge concentrated scale of metallurgical industry, the heat that the energy of this high-temperature tail gas is enough to provide with nuclear reactor is matched.If by current smelter traditional method, be used for pushing turbine by tail gas boiler develops steam vapor and generated electricity by steam turbine drive electrical generators, then electric power is used for metallurgy, then its final thermo-efficiency is only about 25%.If with the high-temperature steam that it produces, implement the hydrogen manufacturing of electrolysis high-temperature vapor, final thermo-efficiency then can bring up to more than 50 ~ 80%.If by the present invention, high temperature electrolysis of steam hydrogen manufacturing, every cubic metre of power consumption≤2kw.h, than current alkaline electrolytic bath water electrolysis hydrogen producing, every cubic metre of hydrogen power consumption 4.5 ~ 5.5kw.h, can save energy more than 50% again here.Like this, natural gas hydro-cracking metallurgy is changed high temperature electrolysis of steam hydrogen manufacturing with its high-temperature tail gas combine, just metallurgy can be smelted iron the consumption of Sweet natural gas by 200 cubic metres of/ton of iron, be reduced to below 100 cubic metres of/ton of molten iron, until also hydrogen metallurgy can be realized without Sweet natural gas completely.This just makes the large national capital of metallurgy of any annual output more than hundred million tons can implement hydrogen metallurgical technology.And the too large pressure of natural gas supply can not be subject to therefrom.If in the place that water energy wind energy etc. can be enriched in production-goods source very much, this has more very important meaning.Because it also likely utilizes flood peak period and monsoon animated period, the electric power that the peak and low valley of night, Holidays wastes usually, for ultra-large electrolytic hydrogen production, stores, and annually balancedly to utilize.The utilization ratio of the renewable energy sources such as water globe energy wind energy is likely improved nearly 1 times by this.This is a marvelous power-saving technology, is a strategic cleaner production of earth shaking national level and energy-saving and emission-reduction measure.

5, " the hydrogen plasma cracking hydrogen manufacturing of the perhydrous coal such as brown coal and plant drymeal ": its principle is

The perhydrous coal such as brown coal and plant drymeal → fugitive constituent+C+

Fugitive constituent → H ₂+ CH ₄+ C ₂h ₂+ C ₂h ₄+ CO+

CH ₄→C+2H ₂

C ₂H ₂→2C+H ₂

C ₂H ₄→2C+2H ₂

Selected by the fine purifiation of hydrogen content >4% drying to mill the perhydrous coal dry powder such as brown coal, or the plant drymeal of hydrogen content >6% comprise forestry, fuel wood, bamboo class, herbaceous plant, branch, fallen leaves, wood chip, wood shavings; Agricultural, stalk, husk, shell, corn cob, bagasse, reed, particularly algae cultivate fast and fish for, to mill the dry powder of obtained <0.1mm through shredding 00 ~ 300 DEG C of drying, drying dehydration is milled straight granularity <0.1mm, and do carrier gas with hydrogen or hydrocarbon fuel gas, smelt pyrolyzer by the hydrogen released in the present invention, all successfully can be cracked into hydrogen and carbon black smelts molten iron discharging simultaneously; This also opens a path for coal enters hydrogen field of metallurgy.

Two, the present invention's it " hydrogen is metallurgical ", the hydrogen mainly adopting the present invention to release smelts pyrolyzer, the metallurgical rotary kiln of hydrogen and metallurgical waste heat high temperature electrolysis of steam groove heap, ensure that hydrogen metallurgy principle can be out and out from theory transition Deng three key equipments, manual intervention, regulation and control can be carried out, can be effective, scale operation can be realized, can to win victory in long-term highly reliable operation, economically worthwhile and market competition, the metallurgical and hydrogen energy source Industrial processes of hydrogen.

Certainly, the electric supplementary heating fluidized-bed proposed in No. 200710085169.1 patent applications or other various effective shaft furnace, rotary kiln, fluidized-bed, rotary hearth furnace etc., only need improve its sealing property, the requirement making it to meet hydrogen reduction also can be used for the reduction process in the hydrogen metallurgy of the present invention, also the scope of the invention is belonged to, but, except the metallurgical rotary kiln of the hydrogen released in rotary hearth furnace and the present invention, shaft furnace and fluidized-bed etc. all can not adapt to the requirement of more than 1200 ~ 1450 DEG C high temperature fast restores, thus efficiency is lower, and energy consumption is higher; And uniquely can match in excellence or beauty with the present invention in efficiency just only have rotary hearth furnace, and rotary hearth furnace because of area of dissipation excessive, thermo-efficiency is not high, can not meet requirement that is metallurgical and the necessary ultra-large production of energy industry.Therefore recommend to adopt the metallurgical rotary kiln of hydrogen.

Now by as follows for hydrogen metallurgy method enumeration:

1, a kind of hydrogen metallurgy method, its technology contents is:

The fast basic technology circulation of (1) two step three:

The first step, with the metallurgical pre-reducing furnace of hydrogen to iron ore concentrate pellet, comprising the granulate particle diameter that obtains of 5 ~ 15mm iron essence lump ore pellet or Iron concentrate ore deposit, market is the Iron concentrate ore particle material of 5 ~ 20mm, carries out Fu Qing H ₂>=80%, high temperature 1200 ~ 1400 DEG C, high pressure 0.2 ~ 2MPa, quick prereduction, produces the sponge iron of reduction degree>=70%; The granulate particle diameter that obtains of the market fine grinding selected Iron concentrate ore deposit of preferred employing granularity <0.1mm is the selected iron ore concentrate pellet of 5 ~ 20mm, carries out Fu Qing H ₂>=90%, low temperature 700 ~ 1200 DEG C, high pressure 0.2 ~ 2MPa, quick prereduction, produces the sponge iron of reduction degree>=80%, all flows to hydrogen metallurgy smelting pyrolyzer to be incubated air-tight manner;

Second step, smelts pyrolyzer with hydrogen metallurgy, realizes Sweet natural gas or coal-seam gas, shale gas, underground gas maked coal, biogas, combustible ice gasification gas; And fine purifiation selects drying to mill perhydrous coal dry powder, the plant drymeals such as brown coal, comprises the plasma rapid cleavage hydrogen manufacturing of algae dry powder etc., produce sponge iron for the quick prereduction of hydrogen metallurgical pre-reducing furnace rich, high temperature hydrogen and hydrogen source is provided; The carbon black simultaneously utilizing cracking to produce manufactures melting high temperature saturated carbon containing iron liquid; Thus realize Flashmelt reduction and the slag sluicing system eventually of the sponge iron to the metallurgical pre-reducing furnace input of hydrogen simultaneously, produce molten iron or half steel; Thus complete the fast basic technology circulation continuous seepage of metallurgical two steps three of hydrogen; Be equipped with hydrogen or hydrocarbon fuel gas does carrier gas, by its coreless armature formed jet through its more than 3000 DEG C high temperature direct current plasma arc arc cores under high temperature condition moment rapid cleavage be high temperature hydrogen, with high temperature carbon black, high temperature hydrogen exports directly supply with tail gas form and produces sponge iron; Enter the manufacture of melting high temperature iron liquid melt pool,

(2) metallurgical waste heat high-temperature water vapour electrolytic hydrogen production: utilize hydrogen metallurgical pre-reducing furnace high temperature height enthalpy using waste heat from tail gas, produce 600 ~ 1000 DEG C of high-temperature vapors, again with proton conductor solid electrolyte high temperature electrolysis of steam groove heap, or oxygen ion conductor solid electrolyte high temperature electrolysis of steam groove heap, to produced high-temperature vapor, implement less energy-consumption high-temperature water and steam electrolytic hydrogen production; The pure hydrogen of high temperature wherein obtained by proton conductor solid electrolyte high temperature electrolysis of steam groove heap, directly can feed back to the metallurgical pre-reducing furnace of hydrogen, as the supplemental hydrogen source of producing sponge iron, the hydrocarbon fuel gas consumptions such as the Sweet natural gas of molten iron per ton are reduced to 100m ³below; And the hydrogen obtained by piling with oxygen ion conductor solid electrolyte high temperature electrolysis of steam groove, containing a large amount of water vapour, need purify through the exhaust treatment system refrigerated separation of this metallurgical system, and again heated up by interchanger heat absorption, then the metallurgical pre-reducing furnace of hydrogen of feeding again is returned, its by-product oxygen drying process recoverable;

(3) tail gas separation and CO transformation and hydrogen production: to producing the metallurgical pre-reducing furnace tail gas of hydrogen after water vapor cooling through heat exchange, proceed dedusting, heat exchange, bag filter, washing, desulfurization, CO conversion, gas delivery, reclaim hydrogen, carbonic acid gas, nanometer carbon black, argon and sulphur; By reclaimed technical pure hydrogen, the hydrogen cooling system of the metallurgical cracking smelting furnace of part feed-in hydrogen, but hydrogen-cooled and recovery of heat is carried out to the metallurgical cracking smelting furnace of hydrogen, part feed-in tail gas heat-exchange system carries out heat absorption and heats up, and then hot for two portions hydrogen is all fed back to the metallurgical pre-reducing furnace of hydrogen, the hydrogen energy source that the cold technical pure hydrogen of flap portion can directly export as hydrogen energy source automobile without the need to heat absorption intensification; The argon reclaimed, then open for system device, stop, keep in repair, pressurized seal and hydrogen metallurgical cracking smelting furnace forehearth is when tapping a blast furnace and slag tap, drive away wherein air, and as the depolarize gas etc. of solid electrolyte high-temperature water vapour electrolytic groove, can recycle and reuse repeatedly.

2, the hydrocarbon fuel gas cracking hydrogen metallurgy method such as a kind of Sweet natural gas as above, coal-seam gas: be adopt the hydrocarbon fuel gas such as desulfurization dewatering Sweet natural gas, coal-seam gas, underground gas maked coal, shale gas, biogas, combustible ice gasification gas to do hydrogen feedstock, its consumption is 0 ~ 200m ³/ t (molten iron) Sweet natural gas or the suitable various hydrocarbon fuel gas of hydrogen content, the central duct of cracking furnace zone check valve high strength coreless armature is smelted by hydrogen metallurgy, with 1 ~ 6m/s jet, through the smelting direct current plasma electric arc arc core of temperature more than 3000 DEG C of powerful, more than 1300 DEG C are just heated to the moment of 0.5 ~ 2 millisecond, under high temperature condition, hydrocarbon fuel gas will be all high temperature hydrogen and nanometer carbon black by rapid cleavage, the trace amounts of CO that may exist in combustion gas ₂also will be reduced to CO by high-temperature nano carbon black, scission reaction time <0.5ms, average reaction temperature 1300 ~ 1600 DEG C, reaction pressure 0.2 ~ 2Mpa, lower pressure is conducive to scission reaction, cracking energy consumption about 3 ~ 4MJ/Nm ³, hydrogen metallurgy is smelted pyrolyzer and is mainly adopted unlimited molten bath standard or the operation of submerged-arc smelting standard, the carbon black that cracking produces is at jet mass force, under Arc effect, at high temperature foam slag, slag, sponge iron shroud covering under, directly enter in the melting high temperature iron liquid below coreless armature, become the dissolved carbon in melting high temperature iron liquid, thus produce sponge iron Flashmelt and reduce necessary high-temperature fusion saturated carbon containing iron liquid, directly to be fallen into from the high-temperature sponge iron of the metallurgical pre-reducing furnace input of hydrogen by the hydrogen metallurgy one or more filling tubes smelted pyrolyzer bell or this melting high temperature saturated carbon containing iron liquid is progressively fused in branch layering, realize Flashmelt reduction slag sluicing system immediately and smelt molten iron discharging or half steel, realize the less energy-consumption Flashmelt reduction metallurgical process of sponge iron, the metallurgical sponge iron usually adopting reduction degree >90% of combustion gas cracking hydrogen, the CO<50kg that melting and reducing ton iron produces, the small part of the hydrogen that cracking produces participates in the reduction reaction of non-reducing iron oxides in sponge iron, the overwhelming majority smelts pyrolyzer tail gas relief outlet and the direct mode of communicating of metallurgical pre-reducing furnace reducing gas input aperture two stove of hydrogen with high-temperature tail gas form and hydrogen metallurgy, directly flow to the metallurgical pre-reducing furnace of hydrogen, fast restore produces sponge iron, thus realizes hydrogen metallurgical technology circulation continuous seepage,

When reduction degree>=80% by sponge iron, ton iron Sweet natural gas add-on <170m ³time, the hydrogen manufacturing of metallurgical waste heat high temperature electrolysis of steam need be implemented in the present system, with the insufficient section of supplementary cracking hydrogen; When enforcement ground water power, wind-powered electricity generation, nuclear power aboundresources, when particularly peak and low valley electric power resource enriches cheap, whole hydrogen metallurgical waste heat high-temperature vapor then can be utilized to carry out electrolytic hydrogen production, also institute's hydrogen manufacturing can be stored in the peak and low valley phase and utilize with post-equalization, institute's hydrogen manufacturing is enough to the hydrocarbon fuel gas consumptions such as Sweet natural gas to reduce to 100m ³/ t (molten iron) below, is even zero, but for zero time need add 30 ~ 70kg/t pure carbon powder replace carbon in Sweet natural gas to meet the carbon needed for carburizing sponge iron, sponge iron melting and reducing and molten iron carburizing.

When the reduction degree of sponge iron is 70 ~ 80%, Sweet natural gas add-on>=170m ³during/t, need not implement residual heat high-temperature water vapour electrolytic hydrogen production in the present system, the hydrocarbon fuel gas such as simple dependence Sweet natural gas can realize hydrogen metallurgy, and this is suitable for comparatively tight or that its price the is higher area of the resourceful area of the hydrocarbon fuel gas such as Sweet natural gas or water power, wind-powered electricity generation, nuclear power resource and implements the present invention.

Conventional carbon dioxide emissions object of the present invention is a ton iron 0 ~ 300kg, and when reducing emission standard further, above-mentioned range of choice adjusting range can be larger.

3, the perhydrous coal such as a kind of brown coal as above and plant drymeal cracking hydrogen metallurgy method: adopt the perhydrous coal such as brown coal and plant drymeal to comprise the raw material as cracking hydrogen production such as algae dry powder, when adopting the perhydrous coal such as brown coal, hydrogen content>=4%, ash <2%, sulphur phosphorus content <0.2% need be adopted, moisture content <1%, the fine purifiation of granularity <0.1mm selects drying to mill the perhydrous coal dry powder such as brown coal dry powder, and its amount of allocating into is 50 ~ 150kg/t (molten iron), when adopting plant drymeal to make hydrogen feedstock, need by the seasoning of desliming roots of plants cauline leaf, chopping, through 200 ~ 300 DEG C of high temperature drying dehydrations, mill and become the dry powder of granularity <0.1mm, its amount of allocating into is, 100 ~ 250kg/t (molten iron), and two kinds of every kilogram, dry powder all need to join 1 ~ 3Nm ³hydrogen or hydrocarbon fuel gas do carrier gas, the central duct of cracking furnace zone check valve high strength coreless armature is smelted by hydrogen metallurgy, with 1 ~ 6m/s jet, through the smelting direct current plasma electric arc arc core of temperature more than 3000 DEG C of powerful, under smelting pyrolyzer high temperature condition, perhydrous coal dry powder, the plant drymeals etc. such as brown coal will be all hydrogen, hydrocarbon gas, carbon black, charred ashes, CO, CO by rapid cleavage ₂, N, water vapor, etc. very complicated composition, wherein hydrocarbon gas extremely unstable under hot conditions more than 1300 DEG C, will continue to be decomposed into hydrogen and carbon black, CO ₂also CO will be reduced to by high temperature carbon black, carbon black, burnt at jet mass force, under Arc effect, at high temperature foam slag, slag, sponge iron shroud covering under, directly enter in the melting high temperature iron liquid below coreless armature, become the dissolved carbon in melting high temperature iron liquid, thus produce sponge iron Flashmelt and reduce necessary high-temperature fusion saturated carbon containing iron liquid, directly to be fallen into from the high-temperature sponge iron of the metallurgical pre-reducing furnace input of hydrogen by the hydrogen metallurgy one or more filling tubes smelted pyrolyzer bell or this melting high temperature saturated carbon containing iron liquid is progressively fused in branch layering, realize Flashmelt reduction slag sluicing system immediately and smelt molten iron discharging or half steel, realize the less energy-consumption Flashmelt reduction metallurgical process of sponge iron, the small part of the hydrogen that cracking produces participates in the reduction reaction of non-reducing iron oxides in sponge iron, the overwhelming majority smelts pyrolyzer tail gas relief outlet and the direct mode of communicating of metallurgical pre-reducing furnace reducing gas input aperture two stove of hydrogen with high-temperature tail gas form and hydrogen metallurgy, directly flow to the metallurgical pre-reducing furnace of hydrogen, fast restore produces sponge iron, thus realizes hydrogen metallurgical technology circulation continuous seepage.This method is suitable for coal resource and enriches, also has coal bed gas resource or natural gas source but water, wind, nuclear power resource area rich or not on the high side is implemented simultaneously.

The present invention compared with prior art tool has the following advantages:

(1) " the fast method basic technology of metallurgical two steps three of hydrogen circulates " is not only built on existing metallurgical technology basis but also is had great Innovation and development, simple and practical, three kinds of innovative means " hydrogen metallurgy smelts pyrolyzer ", " the metallurgical pre-reducing furnace of hydrogen ", " SOEC high temperature electrolysis of steam groove " solves Sweet natural gas in hydrogen metallurgical process comprehensively, coal-seam gas, underground gas maked coal, shale gas, the fossil fuels such as perhydrous coal such as brown coal and the hydrogen manufacturing of plant drymeal rapid cleavage, iron ore concentrate rich hydrogen high temperature fast restore produces sponge iron, molten iron or half steel are produced in the reduction of sponge iron Flashmelt, three large process difficulties, and three closely cooperates, waste heat mutual circulation utilizes, particularly the plasma cracking hydrogen manufacturing of combustion gas or coal and sponge iron melting and reducing are produced the operation of molten iron or half steel and tooling unites two into one by " hydrogen metallurgy smelt pyrolyzer ", equipment is few, powerful, efficiently, energy-conservation, and adaptability is very strong, and can operate continuously year in year out, current unique interior hydrogen metallurgical technology and equipment replacing blast furnace ironmaking,

(2) energy-conservation: ton iron energy consumption≤12GJ (i.e. 400kg standard coal of the present invention, comprise hydrogen manufacturing, prereduction until melting and reducing produces molten iron or half steel, wherein electric power accounts for 40 ~ 70%), than the ironmaking of our times coke blast furnace and COREX fused reduction iron-smelting, ton iron energy consumption >18GJ (i.e. 700kg standard coal, comprise coking, sintering, blast-furnace smelting, wherein electric power accounts for 40%) energy-conservation more than 40%.Be apparent that the most: world Sweet natural gas produces sponge iron, sponge iron per ton consumes 350 ~ 450 cubic metres of Sweet natural gases, and this hydrogen metallurgy method, then only need 50 ~ 200 cubic metres of Sweet natural gases and the perhydrous coal such as hydrocarbon fuel gas and brown coal and the plant drymeals etc. such as available coal-seam gas, underground gas maked coal, biogas, combustible ice replace Sweet natural gas wholly or in part; The hydrogen manufacturing of metallurgical waste heat high temperature electrolysis of steam, take full advantage of metallurgical waste heat, the energy consumption of every cubic metre of hydrogen is made to drop to 1.3 ~ 2.0kw.h by 4 ~ 5.5kw.h, it is the most energy-conservation a kind of hydrogen production process, it not only can as the supplemental hydrogen source of fossil fuel and plant drymeal cracking hydrogen metallurgy, extremely enrich cheap area in water energy wind energy and peak and low valley electric power resource, also can replace fossil fuel hydrogen manufacturing completely.

(3) reduce discharging: hydrogen manufacturing of the present invention, and the metallurgical whole process carbonic acid gas of hydrogen, sulfurous gas, oxynitride etc., all can reduce discharging more than 80% until level off to zero; Because hydrogen metallurgy must realize Full sealed automatic circulation, therefore its industrial dust discharged is also minimum in existing metallurgical iron smelting method, can set up factories around big city completely;

(4) efficient: under the condition adopting the metallurgical rotary kiln of hydrogen, hydrogen metallurgy enters stove from raw material and just can produce high-quality molten iron within an hour, and current blast furnace ironmaking COREX ironmaking need not must maintain high temperature more than 8 hours like that, for efficient, energy-conservation, lower consumption, reduce costs, laid solid foundation;

(5) high-quality: hydrogen metallurgy does not use coal in a large number, thus also need not adopt that special desulfurization measure of blast furnace ironmaking, just molten iron sulphur phosphorus arsenic content can be reduced within international standard, and make follow-up steelmaking process greatly benefited;

(6) comprehensive benefit, social benefit are good especially: the present invention is a hydrogen metallurgy, the new technology that hydrogen energy source of holding concurrently is produced, and likely make smelter by simple major power consumer, are transformed into hydrogen energy supplied rich and influential family; Smelter may be had to implement the costly carbonic acid gas landfill having no income, be transformed to nanometer carbon black and the high-quality carbon black by-product of high benefit; Because metallurgical industry is very huge and concentrated, the present invention is once realize industrialization, and all large-scale metallurgical enterprises, can oneself carry out, all lucrative, do not have current development hydrogen energy source automobile to need to set up in the whole world hydrogen energy source and produce and generally set up the precondition that gas station is difficult to start to walk.For global hydrogen energy source, development hydrogen economy have found a breach.Metallurgical Carbon emission accounts for about 20% of global carbon dioxide discharge, and first metallurgy realize Carbon emission and level off to zero, and it is to the contribution of human society, and who can not underestimate.

Accompanying drawing explanation

Fig. 1 is " hydrocarbon fuel gas such as Sweet natural gas or coal-seam gas cracking hydrogen metallurgy method " process flow diagram;

Fig. 2 is " perhydrous coal and the plant drymeal cracking hydrogen metallurgy method such as brown coal " process flow diagram;

Fig. 3 is " hydrogen metallurgy smelts pyrolyzer " structural representation;

Fig. 4 is " hydrogen metallurgy smelts pyrolyzer, the coreless armature of band check valve " structural representation;

Fig. 5 is " hydrogen metallurgy smelts pyrolyzer, electrode insulation location current collection tightness system " structural representation;

Fig. 6 is " hydrogen metallurgy smelts pyrolyzer, hydrogen-cooled annular cylinder electrode lifting device " structural representation;

Fig. 7 is " hydrogen metallurgy refining pyrolyzer, the high insulation hydraulic efficiency slide valve formula mouth of a river (cinder notch) " structural representation;

Fig. 8 is " hydrogen metallurgy refining pyrolyzer forehearth " structural representation;

Fig. 9 is " the metallurgical rotary kiln of hydrogen " structural representation;

Figure 10 is " SOEC proton conductor high temperature electrolysis of steam groove " structural representation;

Figure 11 is " SOEC tubular type electrolysis list pond " structural representation;

Figure 12 is " SOEC high temperature electrolysis of steam groove " Structure of cross section schematic diagram shown in Figure 10;

Figure 13 is " SOEC oxygen ion conductor high temperature electrolysis of steam groove " structural representation.

Embodiment

Now the present invention is further illustrated in conjunction with the accompanying drawings and embodiments:

Embodiment one, " hydrocarbon fuel gas such as Sweet natural gas or coal-seam gas cracking hydrogen metallurgy method " embodiment (accompanying drawing 1, dotted line in figure, then represent: utilizable hydrogen feedstock, the water wind power station peak and low valley electric power of striving utilizing, the operation that can increase or strive to apply, can the product of attached product):

Iron-smelting raw material: the selected fine iron breeze in LiaoNing, China Anshan: TFe66.3%, MnO0.3%, SiO ₂1.2%, Al2031.03%, CaO1.79%, MgO0.79%, S0.02%, P0.017%.Granularity 200 order accounts for 90%; This is the selected fine iron breeze in a kind of typical market, instead of through the iron ore concentrate superfine powder of special processing.When " the electric supplementary heating fluidized-bed " that propose in employing No. 200610106689.1 patent applications or other fluidized-bed carry out prereduction as " the metallurgical pre-reducing furnace of hydrogen ", then directly can use this dry fine ore; When " the metallurgical rotary kiln (accompanying drawing 9) of hydrogen " that adopt in the present invention or other pre-reducing furnace, during as shaft furnace etc., the pellet that 10 ~ 20mm made by the binding agent nodulizer that this breeze must be added 3 ~ 5% is applied after drying.The present embodiment adopts the latter.

Hydrogen feedstock: the present embodiment adopts Shanxi Province, China coal-seam gas, and (its typical composition is: CH ₄96.52%, CO ₂0.45%, N ₂3.03%, H ₂s<20mg/m ³) or Sichuan Province China Sweet natural gas (its typical composition is: CH ₄97.78%, C ₂h ₆0.64%, C ₃h ₈0.15%, CO0.03%, H ₂0.09%, N ₂0.12%, CO ₂0.1%, H ₂s<10mg/m ³); Enter stove proportioning, the choosing comprehensively such as carbon emission standard, enterprise's optimum economic benefit target, process specifications that can limit according to the resource of enterprise, government is at 80 ~ 200m ³adjust within the scope of/t.The present embodiment is finally determined to adopt Shanxi coal-seam gas, and it enters stove proportioning and orders as 100m ³/ t (t refers to 1 ton of molten iron, lower same).

Major equipment: " hydrogen smelting pyrolyzer " is a kind of " the hydrogen-cooled direct current plasma high-pressure hollow electrode arc stove of band forehearth " (accompanying drawing 3) in the present embodiment, select the reason of this electric arc furnace, because it can realize various combustion gas cracking hydrogen production task, high-quality molten iron and half steel are produced in the melting that simultaneously can complete again sponge iron eventually reduction, and can operate continuously year in year out as the blast furnace and perform extensive ironmaking task, efficient, energy-conservation, " the metallurgical pre-reducing furnace of hydrogen ", then adopt " the metallurgical rotary kiln of hydrogen " (accompanying drawing 9) released in the present invention, shaft furnace conventional in itself and metallurgical industry, fluidized-bed, compare, the equipment uniquely can implementing more than the 1200 DEG C quick prereduction of high temperature, although rotary hearth furnace more can adapt to this operational condition, but area of dissipation is excessive compared with rotary kiln, volumetric efficiency is too low, facts have proved in recent years, rotary hearth furnace can not be applicable to the extensive Iron and Steel Production producing millions of tonnes per year, and in Chinese Tianjin Steel Pipe Corp., rotary kiln facts have proved that it has this ability.And " the metallurgical rotary kiln of hydrogen " takes multiple anti-ring formation measure and resist melt slag iron bonding erosion measure, as adopted the high top pressure operation of 1Mpa, improve the concentration of hydrogen, spread coefficient, with reduction reaction velocity constant, be very beneficial for the reduction of FeO, reduce the bonding tendency of furnace charge, add in furnace charge there is no the low-melting carbon of ash, experiment proof " the metallurgical rotary kiln of hydrogen " is at the high pressure of 1Mpa, high temperature between 1200 ~ 1350 DEG C pure hydrogen iron ore concentrate pellet fast restore, dross, the possibility of ring formation is very little, in order to perfectly safe, " the metallurgical rotary kiln of hydrogen " have employed resist melt slag, iron bonds, the silicon nitride combined silicon carbide furnace lining corroded, strengthen the monitoring of kiln temperature and kliner coating temperature, can the temperature adjustment of segmentation in time process it be made to recover normal once not normal, the electric supplementary heating device of its high temperature section also can be heated to 1600 DEG C of high temperature, ring formation can be fused into molten iron under without the need to the operating mode of blowing out to enter " hydrogen smelting pyrolyzer ", this stove has again huge high-temperature gas surge volume simultaneously, and being that " hydrogen smelting pyrolyzer " prevents spike high pressure overladen ideal buffering stove when performing cracking hydrogen production task, is that shaft furnace etc. is difficult to replace, " SOEC high temperature electrolysis of steam groove " employing " SOEC proton conductor high temperature electrolysis of steam groove " (accompanying drawing 10), also can adopt " SOEC oxygen ion conductor high temperature electrolysis of steam groove " (accompanying drawing 13).The former advantage can directly export pure hydrogen, and produced high temperature height enthalpy hydrogen directly can be inputted the metallurgical pre-reducing furnace of hydrogen, high energy saving, also eliminate water vapour refrigerated separation operation, flow process is short, efficiency is high.The advantage of the latter is that novel material solid electrolyte YSZ applies more in a fuel cell, and manufacturing cost is lower.The present embodiment is according to development viewpoint, and energy-conservation, efficient viewpoint, determines to adopt " SOEC proton conductor high temperature electrolysis of steam groove "; " exhaust treatment system ", be adopt the conventional tail gas treatment device in existing metallurgical system: as gravitational precipitator, bag filter (carbon black separation), Venturi meter, washing tower, water trap, fine de-sulfur device, CO transmodulator, pressure swing adsorption gas separation device, and the compositions such as output equipment processed by carbon black.In native system, each major equipment all arranges static eliminator, hydrogen leaks monitoring instrument, the safety dumping pipe etc. of safety valve, Waste gas outlet, spark arrester and energy coutroi velocity;

Device systems: by high-pressure stop valve, reducing valve, tensimeter, flowrate control valve, mass flowmeter in the hydrocarbon fuel gas supply systems such as coal-seam gas, reversing valve, high pressure hose, high-pressure hose connector, couple together with " being with the electrode contact of check valve " (7 in Fig. 3) of " smelting pyrolyzer " coreless armature (6 in Fig. 3) upper end; Supply lock-hopper system by the opening for feed of " the metallurgical pre-reducing furnace of hydrogen " and iron ore concentrate pellet to couple together; And connect all relevant devices by accompanying drawing 1.Native system just can run.

Smelting operation: before system energization runs, first must drive away air in whole metallurgical system all devices to guarantee safety with argon gas.In " hydrogen smelting pyrolyzer ", enough opening arc and manufacture initial melting and reducing iron should be put into according to the size of stove and bathe necessary steel scrap, sponge iron; Start power supply system, transfer its electrode, melted, make melting high temperature iron liquid molten bath (iron bath); Again by Shanxi coal-seam gas, in setting ratio, formed the jet of 1 ~ 6m/s by the central duct of coreless armature, more than the 3000 DEG C direct current plasma electric arc arc cores that ingoing power is powerful, namely the moment of several milliseconds is heated to more than 1600 DEG C, under high temperature condition, Shanxi coal-seam gas will all be broken down into high temperature hydrogen and nanometer carbon black, the small part of hydrogen participate in non-reducing iron oxides in sponge iron, etc. reduction reaction, major part is with high-temperature tail gas form, insulation air-tight state, exports electric arc furnace; Carbon black directly enters the dissolved carbon becoming melting high temperature iron liquid in the melting high temperature iron liquid below coreless armature under the covering effect of jet mass force, Arc and slag, foamy slag, thus produce sponge iron Flashmelt and reduce necessary high-temperature fusion saturated carbon containing iron liquid, participate in sponge iron melting reduction eventually, also can by CO in furnace gas ₂also reduction becomes CO." hydrogen smelting pyrolyzer " smelts function aspects in execution, and unlimited molten bath standard or long arc foamy slag formula both can have been adopted to operate; Also can perform submerged-arc smelting operation, and the present embodiment adopts the former, to implement Flashmelt reduction.Here it is, more than the 1000 DEG C high temperature of airtight input from " the metallurgical pre-reducing furnace of hydrogen " are incubated from the feed-pipe " hydrogen smelting pyrolyzer " bell, more than 95% high reduction degree sponge iron, to directly fall into this high-temperature fusion saturated carbon containing iron liquid, wherein reduced iron will be promptly melted and realize slag sluicing system and produce molten iron; Wherein the dissolved carbon be saturated in carbon containing iron liquid is also reduced the alloy ingredient become in molten iron or molten iron by still unreduced ferric oxide, manganese oxide, part of silica etc., and discharges carbon monoxide and mix with hydrogen and export.Saturated carbon containing iron liquid reducing iron oxides produce the speed of molten iron than blast furnace solid carbon reducing iron oxides more than fast ten times, and this is the feature of melting and reducing, are also a high production efficiency.In the present system, we can control hydrocarbon fuel gas additional proportion and spongy iron reducing degree to the scale of the work output and foamy slag that control carbon monoxide and carbon black.In the present embodiment, due to Sweet natural gas input deflection low side, the reduction degree >95% of input sponge iron, therefore carbon black output levels off to zero.Because the present invention is without coal, and commodity coal-seam gas, Sweet natural gas, sulphur content is very low, usually without phosphorus in the gas maked coal of underground, by international standard S<20mg/m ³, in merchant iron fine ore, sulphur phosphorus arsenic content is also very low simultaneously, and therefore hydrogen metallurgy method not only can need not take that extra secondary desulfurization dephosphorization measure of blast furnace ironmaking completely, and its Sulfur Content in Hot Iron phosphorus content is all far below blast-melted; And sulphur content in vent gas treatment is also very little from treatment capacity.The iron liquid produced is exported by forehearth.Why " hydrogen smelting pyrolyzer " needs forehearth, this is because hydrogen air is mixed than in 4 ~ 75% scopes, all may produce blast.Be filled with High Temperature High Pressure hydrogen in " hydrogen smelting pyrolyzer ", therefore definitely can not allow that air mixes and also not allow that hydrogen leaks, this is also the maximum difficult point of hydrogen metallurgy.If when " hydrogen smelting pyrolyzer " directly taps a blast furnace and slags tap, be difficult to avoid hydrogen to leak, certainly we can drive away with rare gas element that wherein taps a blast furnace after hydrogen again slags tap, but can cause discontinuous production and reduce efficiency, and smelt iron on a large scale must running continuously.Therefore the present invention not only devises forehearth, and devise ladle valve between forehearth and main stove and or cinder notch, by cut off the mouth of a river and or cinder notch, just independently can operate forehearth, comprise and displace wherein hydrogen and then open forehearth iron mouth and tap a blast furnace and slag tap with argon, and now main stove can operate continuously always.

In the present embodiment, iron ore concentrate pellet, from the lock-hopper system feedstock supply unit, after entering " the metallurgical rotary kiln of hydrogen ", implements pure hydrogen H ₂>=96%, high temperature (1000 ~ 1350 DEG C, approach high-end under the condition of iron ore concentrate composition not ring formation as far as possible, to make every effort to improve reduction rate, here it needs to be noted, owing to using the selected fine iron breeze pellet of granularity <0.1mm in the present embodiment, rich hydrogen reduction, experiment proves, they are usually between 1000 ~ 1200 DEG C, just can at the reduction degree realizing more than 90% within an hour, this is concerning " hydrogen metallurgical rotary kiln " normal work, normal work does not have hell and high water certainly, smelt the direct of pyrolyzer with hydrogen metallurgy to be connected, even can without the need to electric supplementary heating), high pressure (1.0 ± 0.2Mpa, ) fast restore.Under such reaction conditions, the seepage force reducing power of hydrogen is very strong, the speed of its reducing iron oxides, faster than the CO reduction rate of current conventional shaft furnace, rotary kiln, fluidized-bed more than 5 times, with above-mentioned iron ore concentrate pellet, by hydrogen reduction to more than 95%, in most cases can will reach 98% within 1 hour, reducing sponge iron is sent to " hydrogen smelting pyrolyzer " at the direct stream of insulation air-tight state.This is again a high production effect speed, and the reduction of common rotary kiln, reduction shaft furnace, all more than 10 hours.

In the present embodiment, when smelting pyrolyzer and exporting molten iron, directly pre-reducing furnace is flowed to by there being the high temperature height enthalpy tail gas of temperatures as high more than 1200 DEG C.When pre-reducing furnace exports sponge iron, will have 1100 DEG C, the high-temperature tail gas of more than 50k.mol/t exports, and by gasification cooling flue, just can obtain 900 DEG C, more than 40k.mol/t high-temperature vapor.This high-temperature vapor is sent into " SOEC proton conductor high temperature electrolysis of steam groove ", carries out electrolysis and at least can obtain 20k.mol/t (400Nm ³/ t) the pure hydrogen of above hot industry.These high temperature height enthalpy technical pure hydrogen can directly input again " the metallurgical pre-reducing furnace of hydrogen ".

The tail gas of " the metallurgical pre-reducing furnace of hydrogen " after gasification cooling flue heat exchange cooling, and " SOEC high temperature electrolysis of steam groove " tail gas, send into " exhaust treatment system ", proceed gravitational dust collection, heat exchange cooling, bag filter, washing, desulfurization, CO conversion, gas delivery, reclaim hydrogen, carbonic acid gas, nanometer carbon black, argon and sulphur; By the cold technical pure hydrogen of institute's Separation and Recovery, partly (supply the H of 50Kmol/t needed for hydrogen-oxygen metallurgical rotary kiln ton iron ₂wherein more than 50% is recycle hydrogen) the hydrogen cooling system of input " hydrogen metallurgy smelt pyrolyzer ", with tail gas heat-exchange system, because the thermal conductivity of hydrogen is very high, thus, can carry out effective cooling to " hydrogen metallurgy smelts pyrolyzer " on the one hand, the standard of effective cooling is that its nexine such as cupola well, slag line refractory materials working temperature controls between 1000 ~ 1100 DEG C, to ensure that it reliably runs with long-lived; The heat that energy effective recycling on the other hand " hydrogen metallurgy smelts pyrolyzer " is distributed, " the metallurgical pre-reducing furnace of hydrogen ", " SOEC high temperature electrolysis of steam groove ", using waste heat from tail gas, hot hydrogen after preheating also feeds back to " the metallurgical pre-reducing furnace of hydrogen ", thus has lowering consumption and environment protecting of joint better than existing metallurgical furnace water cooling plant (heat energy that its water coolant absorbs has wasted usually).Reclaim hydrogen flap portion can be used for the hydrogen energy source of answering market as hydrogen energy source automobile, the hydrogen energy source production function of Here it is hydrogen metallurgy.The carbonic acid gas limited amount reclaimed, can supply market as Industrial products, obtains certain economic return; When the argon reclaimed then opens and closes as system device and keeps in repair, drive away the rare gas element of wherein air, and as " SOEC proton conductor high temperature electrolysis of steam groove " depolarize gas etc., can recycle and reuse repeatedly; Verify reality factually, the energy consumption of the every mol hydrogen of natural gas pyrolysis hydrogen manufacturing is only about 38KJ, and far below the 63.3KJ of vapor reforming hydrogen production, namely the present embodiment cracking hydrogen is about 10k.mol/t, and total energy consumption is 0.38GJ/t; " SOEC proton conductor high temperature electrolysis of steam groove " brine electrolysis steam hydrogen production, every cubic metre of energy consumption <2kw.h, far below 4.5 ~ 5.5kw.h of existing alkaline electrolytic bath water electrolysis hydrogen production, the i.e. 20k.mol/t of high temperature electrolysis of steam hydrogen manufacturing in the present embodiment, energy consumption is no more than 2.0GJ/t; Coal-seam gas 100NM ³/ t, amounts to 3.6GJ/t; Sponge iron is produced in the metallurgical rotary kiln prereduction of hydrogen, its thermal source mainly smelts the heat of the pure hydrogen of high temperature obtained by the heat of pyrolyzer high-temperature tail gas and high-temperature electrolysis water vapour from hydrogen metallurgy, and hydrogen-cooledly change heat reclamation heat-production energy, in any case electricity supplementary heating and the energy that mechanical transmission consumes can not more than 500kw.h/t, i.e. 1.8GJ; And the energy consumption of high-temperature sponge iron melting whole reducing slag iron separation of produced molten iron discharging also can not more than 500kw.h/t, i.e. 1.8GJ/t, therefore the present embodiment ironmaking whole process total energy consumption is lower than <10GJ/t, than the total energy consumption >18GJ/t energy-conservation more than 45% of current huge coke blast furnace ironmaking.The knack of its high energy saving is to reduce as far as possible operation, reduces the cooling repeatedly of raw material, product and tail gas and repeatedly heat, and with the heat that all recuperable waste heats of hydrogen retrieval and smelting pyrolyzer etc. distribute, both saved the longevity that the energy also ensure that stove; Its greatest benefit is need not extra Mitigation options, and its carbonic acid gas, sulfurous gas, discharged nitrous oxides all level off to zero.Virtually saved overspending and cost, this is the target that all ironmaking technologies existing there is no method realization.

When enforcement ground, electricity price is higher, and coal-seam gas, natural gas source are abundant, then the proportioning of the hydrocarbon fuel gas such as Sweet natural gas can be brought up to 180 ~ 200 cubic metres of/ton of iron, then can not implement high temperature electrolysis of steam hydrogen manufacturing and also can realize hydrogen metallurgy, its Carbon emission≤200kg/t, at this moment, the present invention has become a kind of " combustion gas cracking hydrogen metallurgy method " merely.This is the situation of the present invention electric power regional enterprise relatively in short supply for Sweet natural gas enriches.When high-temperature water vapour electrolytic hydrogen production amount is more than 300Nm ³during/t, by the present invention, can not implement natural gas pyrolysis hydrogen manufacturing and also can realize hydrogen metallurgy, at this moment, the present invention has become a kind of " residual heat high-temperature water vapor electrolysis hydrogen metallurgy method " merely, but still necessary pure carbon dust few in number need be added according to the requirement of molten iron carbon content and spongy iron reducing degree and emission standard, this is suitable for water, wind, nuclear energy electric power resource enrich inexpensive area especially.

Embodiment two, " perhydrous coal or the plant drymeal cracking hydrogen metallurgy method such as brown coal " embodiment, accompanying drawing 2:

Iron-smelting raw material: market common iron essence lump ore pellet: TFe62.5%, SiO24.5%, Al2032.9%, S0.02%, P0.07%.Granularity 5 ~ 10mm.Also can use the various Iron concentrate ore deposit of domestic and international market, comprise the selected fine iron breeze of granularity <0.1mm, add 10 ~ 20mm iron ore concentrate drying and dehydrating pellet that a small amount of binding agent manufactures.

Hydrogen feedstock: one washes keen-witted and capable dry brown coal dry powder of milling, composition (wt): C69.1%, H5.5%, 020.8%, N1.4%, S0.1%, ash 2.5%, coal powder size <0.1mm; Also can adopt water content≤1%, the chopping drying of same particle sizes is milled plant drymeal.Entering stove proportioning is that fine purifiation selects brown coal dry powder 100kg/t or plant drymeal 150kg/t.

Metallurgical equipment System's composition is substantially identical with embodiment two, and only needing hydrocarbon feeding mechanism to change into hydrocarbon is coal dust is inputted in stove by carrier gas device by " hydrogen metallurgy smelts pyrolyzer " centre hole of electrode.And be plasma working gas with hydrocarbon, produce hydrogen plasma high temperature.

With " the metallurgical pre-reducing furnace of hydrogen ", here refer in particular to " the metallurgical rotary kiln of hydrogen ", to iron ore concentrate pellet: comprising iron essence lump ore pellet that granularity is 2 ~ 10mm and fine iron breeze or the iron ore concentrate micro mist adding additives particle diameter obtained of granulating is the pellet of 5 ~ 20mm, carry out 1200 ~ 1400 DEG C, 0.2 ~ 2MPa, rich hydrogen H ₂>80%, high temperature fast restore, produces reduction degree >70% sponge iron, directly flows to " hydrogen metallurgy smelts pyrolyzer " to be incubated the direct mode of communicating of airtight two stove

By the coreless armature central duct of " hydrogen metallurgy smelts pyrolyzer ", carrier gas and plasma working gas is made with the hydrocarbon fuel gas such as hydrogen or Sweet natural gas, or make carrier gas and plasma working gas with the mixed gas of hydrogen and argon, select drying brown coal powder by proportioning input iron-smelting raw material fine purifiation, carrier gas dosage is every kilogram of coal 1 ~ 2Nm ³, by carrier gas supercharging, in coreless armature central duct, form 1 ~ 6m.S ^-1jet, through the direct current plasma arc arc core of more than 3000 DEG C of its powerful, under high temperature condition, brown coal will be hydrogen, CO by direct rapid cleavage ₂, CO, water vapour, Jiao, carbon black, ash and H ₂s; Wherein CO ₂to be reduced to CO by Pintsch process carbon, and small part hydrogen, CO, will participate in and the reduction reaction of non-reducing iron oxides in sponge iron, most of hydrogen, CO will export electric arc furnace with high-temperature tail gas form insulation air-tight state; Burnt and carbon black directly enters the dissolved carbon becoming melting high temperature iron liquid in the melting high temperature iron liquid below coreless armature under the effect of himself jet mass force, Arc, carbon black part is free in tail gas and exports with tail gas, and its work output controlled by the actual proportioning of hydrocarbon fuel gas and spongy iron reducing degree; The high temperature height reduction degree sponge iron that " hydrogen metallurgical pre-reducing furnace " produces falls into melting high temperature iron liquid by the charge cavity on insulation closed conduit and " hydrogen metallurgy smelts pyrolyzer " bell and realizes Flashmelt whole reducing slag iron separation of produced molten iron discharging, or float over soft Jiao of melting, slag liquid level more progressively reduction thawing slag sluicing system produce molten iron.

Especially, in the area that perhydrous coal and coal-seam gas or underground gas maked coal, Sweet natural gas all enrich, then can replace hydrogen with coal-seam gas or underground gas maked coal, Sweet natural gas etc. and make carrier gas and plasma working gas.Just can the consumption of corresponding minimizing high-temperature water vapour electrolytic hydrogen, increase the output of energy hydrogen.

Fig. 3 illustrates, a kind of " hydrogen metallurgy smelts pyrolyzer ", this stove is a kind of " the hydrogen-cooled high voltage direct current plasma arc furnace of band forehearth ", there is hydrogen-cooled body of heater 1, and hydrogen-cooled bell 3, between body of heater and bell and all outer Link Ports be equipped with the gasket 2 formed with the austenitic stainless steel leather wallet flexible graphite plate of anti-hydrogen embrittlement, hydrogen-cooled electrode insulation location current collection tightness system 5 is directly installed on the central position of bell 3 by gasket, to be arranged by gasket with prescinding branched ceramic feed-pipe 4 that boron nitride ceramics fibre or silicon carbide ceramic fiber reinforcement reaction sintering silicon nitride material make and stretch into burner hearth around the current collection tightness system of hydrogen-cooled electrode insulation location, hydrogen-cooled annular cylinder electrode lifting device 6 is arranged on the upper surface of hydrogen-cooled electrode insulation location current collection tightness system 5 also with one heart by insulating mat, high strength coreless armature 7 with check valve joint is just arranged on its lower end within hydrogen-cooled annular cylinder electrode lifting device and stretches into burner hearth core area, and available hydrogen-cooled annular cylinder electrode lifting device 6 pairs of coreless armatures are elevated arbitrarily and hover, the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and or cinder notch 8 be arranged in cupola well slag line following molten pig liquid band, the ladle heel sheaf space preventing plasma arc burn furnace bottom is left apart from furnace bottom, before each blow-on, application argon or nitrogen flooding are removed out hydrogen metallurgy and are smelted all air in pyrolyzer and this metallurgical system, and smelt in pyrolyzer at hydrogen metallurgy the steel scrap scrap iron placed enough electric arc furnace starting the arc and damned iron layer space can be filled up after melting, put down electrode direct current arc again to be melted and produce melting high temperature iron liquid molten bath (iron bath), the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and or cinder notch 8 through the forehearth 9 detecting displacement apparatus with gaseous constituent, can operate from forehearth, forehearth 9 is put at the molten iron and slag of smelting iron layer top of can checkmating under pyrolyzer melting continuously condition, disturb for molten iron in reinforcement smelting pyrolyzer and mix, particularly such as only has one when ceramic feed-pipe 4 comparatively small amt, outside furnace shell, just preferably arrange electromagnetism disturb and mix coil 16, the capacity smelting pyrolyzer according to hydrogen is different, the iron mouth that slag iron share can be set, the iron mouth and cinder notch and corresponding molten iron forehearth and slag forehearth that separate also can be set, if be special cinder notch, should open near slag line.

Its hydrogen-cooled body of heater 1 and hydrogen-cooled bell 3 are double-deck high-quality Ultra-low carbon structure iron or low-carbon austenitic structure, Integral sealing compressive strength >5MPa, body of heater bell appearance is common aluminum silicate fiber spray coating heat preservation layer, furnace bottom section is divided in double-layer stainless steel interlayer, cupola well section, shaft section, with bell section, volution is established to cool hydrogen channel in section, the origin or beginning of passage and terminal weld inlet pipe 10 respectively, with escape pipe 13, each inlet pipe connects cooling hydrogen inlet manifold 12 by Electromagnetic Flow variable valve, each escape pipe is then directly connected cooling hydrogen and to be given vent to anger house steward 14, all be embedded with thermopair in each section of furnace lining carry out detection and automatically control, its cooling intensity is, by furnace bottom, cupola well, the working temperature of the innermost layer refractory materials of slag line controls between 1000 ~ 1100 DEG C, impel inner lining surface to form thin layer slag iron and " freeze housing ", body of heater box hat internal surface is provided with the convex tendon keeping refractory materials and strengthen furnace wall, the furnace lining being close to box hat internal surface is prescind sapphire whisker or prescind the mould material that boron nitride fibre and silicon nitride or aluminum nitride powder etc. be mixed, or ramming mass, the high heat conductance height insulation furnace lining of moldable making, body of heater section, the liner of cupola well section contact molten iron and slag is the brick layer of mold pressing ultramicropore silicon nitride combined silicon carbide ceramic cup, furnace bottom section is provided with the conducting hearth copper plate electrode of drawing with the copper rod welding of flanged dish, 3 ~ 4 layers of mold pressing ultramicropore carbon brick are had on conducting hearth copper plate electrode, the superiors are laid on end mold pressing ultramicropore magnesia carbon brick, brickwork joint is less than 1mm, build by laying bricks or stones with high-quality carbonaceous clay.

Fig. 4 illustrates, a kind of hydrogen smelts the high strength coreless armature of the band check valve joint of pyrolyzer,

The high strength coreless armature (7) of described band check valve joint is with high strength isostatic pressed impregnated graphite or Ti3SiC ₂ceramic layered manufacture, and process through precision optical machinery, diameter need smelt pyrolyzer capacity according to hydrogen and the calculating of electrode working current size is determined, Single lead length is 2 ~ 4m, whole electrode is according to electric furnace size, propping up electrode series winding by some lists to form, realizing series winding by being with the electrode contact 41 of check valve; The structure of this electrode contact is: spool 45 is placed in jointing body 44 inner chamber actively, relies on the non-magnetic stainless steel spring 46 on spring support 47 to be resisted against spool rear portion, makes spool shutoff on the opening of fittings body front portion; Its fittings body, spool, spring support all manufacture with described electrode same material, soft graphite O-ring seals 42,43 is provided with between fittings body 44 and noncontinuous electrode 41, carry out the sealing of the mutual end face of electrode and electrode and the mutual end face of electrode contact, ensure that stove inner high voltage hydrogen is unlikely to leak, and to be convenient to after consumption of electrode shortens spreading in addition immediately, during spreading, before fully tightening electrode, application argon gas displaces the air in this extension electrode endoporus, then enters normal work after fully tightening; For increasing the intensity of joint, and be the bore expanding check valve when implementing coal and plant drymeal cracking, described check valve can also make separately and be arranged under hollow connector.

Fig. 5 illustrates, a kind of hydrogen metallurgy smelts pyrolyzer electrode insulation location current collection tightness system:

Hydrogen metallurgy smelts the hydrogen-cooled electrode insulation location current collection tightness system 5 of pyrolyzer, there is the insulation retaining ring body 51 prescinding boron nitride ceramics fibre or the making of silicon carbide ceramic fiber reinforcement reaction sintering silicon nitride, and after assembling therebetween with the ring header body 53 of fine copper or pure nickel or nickel cermet, making, form the hydrogen-cooled electrode insulation location current collection tightness system annular solid of a unification, its Inner Constitution cooling hydrogen circulation passage, and on the bonding surface of the two, be provided with the O shape flexible graphite sealing ring 54,510 preventing cooling hydrogen from leaking, between insulation retaining ring body 51 inner ring surface and high strength coreless armature, the wear ring string 52 that boron nitride ceramics fibre wear ring and flexible graphite sealing ring constitute jointly is respectively equipped with between outer ring surface and bell, 55, ring header body 53 is provided with soft graphite current collection wear ring string 56 with the bonding surface place of coreless armature 7 and compresses with non-magnetic stainless steel swivel nut 57, sealing ring string is except sealing function, prior effect is conduction and heat conduction, therefore the quantity of soft graphite current collection wear ring should be determined according to the working current size of plasma arc and heat calculation, guarantee that there is enough conductive section sum heat-conducting areas.Current collection ring body 53 is also provided with joint 58 that the cooling joint 59 that enters of hydrogen and cooling hydrogen exports and direct current negative pole connects electric pile crown 510;

Fig. 6 illustrates, a kind of hydrogen smelts pyrolyzer annular cylinder lifting device:

Hydrogen metallurgy smelts the hydrogen-cooled annular cylinder electrode lifting device of pyrolyzer, and the upper band-type brake 613 identical by structure and lower band-type brake 614 and hoist cylinder 611 form; The structure of upper and lower band-type brake 613,614: swing on axle that oil motor 62 to be arranged on band-type brake body 61, to swing oil motor 62 and be connected with screw rod 63 with feather key, screw end head is resisted against the brake shoe block 64 for holding coreless armature 7 tightly; The inner ring 65 of hoist cylinder 611 is 3 layers of hydrogen-cooled structure, inside is provided with cooling hydrogen circulation passage, connect firmly with the band-type brake body 61 of lower band-type brake, and constitute jointly annular cylinder with outer shroud 610 etc., the annular words plug of oil cylinder is just mounted in it with annular piston bar 69 and sealing member thereof, and the band-type brake body that piston rod stretches out cylinder body and upper band-type brake 613 connects firmly; The inner ring cylinder body of hoist cylinder 65 is provided with and cools cooling hydrogen air inlet that hydrogen channel is communicated with, air outlet adapter 66,67, outer shroud is provided with hydraulic liquid turnover joint 68,612, all steel annular parts of oil cylinder, all use non-magnetic stainless steel manufacture, oil cylinder anti-flame hydraulic fluid drives.

Fig. 7 illustrates, a kind of hydrogen metallurgy smelts pyrolyzer height insulation hydraulic ceramic ladle valve:

Hydrogen metallurgy smelts the ladle valve 8 of pyrolyzer, is that the large parts series winding of hydraulic ram 78 3 driven by ceramic slide body 76, heat-proof device 77, anti-flame hydraulic fluid is formed; Pottery slide body, is manufactured by spool 71 boron nitride ceramics fibre reinforcement reaction sintering silicon nitride pottery again, and with plasma spraying boron nitride antifriction layer; Internal spool valve cover 72 is also manufactured by boron nitride fiber reinforced reactively sintered silicon nitride ceramics; Be snug sliding fit between spool and internal spool valve overlap, have flexible graphite sealing ring 73 pairs of furnace gases to seal; Moderate soak layer 74 is the ceramic mould material manufactures made from the silicon carbide granular refractory fiber of lower thermal conductivity or nitrogen blowing alumina hollow ball and silicon nitride combined silicon carbide powder, outer installation sleeve 75 is manufactured, with mounting flange by sapphire whisker intensified response sintered silicon nitride ceramic material; The duct that molten iron flows out is opened at middle part after valve pocket, thermal insulation layer, the combination of outer installation sleeve, and can be opened and closed by spool, core bar body 71 stretches in heat-proof device 77, is connected with the piston rod of hydraulic ram 78.

Fig. 8 illustrates, a kind of hydrogen metallurgy smelts the forehearth that pyrolyzer has gaseous constituent detection displacement apparatus and the slag-tapping function that independently taps a blast furnace:

Hydrogen metallurgy is smelted pyrolyzer and is had gaseous constituent and detect displacement apparatus and the forehearth 9 of slag-tapping function of independently tapping a blast furnace, and is to be made up of body of heater 81, bell 83 and the Thin Stainless Steel plate holder flexible graphite sealing pad 82 etc. be clipped between both bonding surface; Insulation ruhmkorff coil 813 can be set outside body of heater, lower portion of furnace body be provided with common iron mouth and or cinder notch 812, be fixedly connected with main stove with web plate 810 grade by flange 811, by ladle valve 8 from main stove input iron liquid and or slag liquid, and can be closed or open at any time as required, between forehearth and main stove, a horizontal height also separately can be established to be incubated hydraulic ceramic guiding valve, to change spool and the valve pocket of " high insulation hydraulic ceramic ladle valve and/or cinder notch "; Bell is provided with hydrogen content detecting sensor 84, pressure, temperature and remote control display and control instrument 89, and is provided with hydrogen delivery valve 85, air diffusion valve 86, spark arrester 87, bleeder 88; Lower portion of furnace body is provided with argon gas input tube 814, stopping valve and porous plug;

The effect of forehearth is to ensure that the metallurgical electric arc furnace of hydrogen taps a blast furnace period not blowing out of slagging tap, and image height stove is the same can long-time continuous running.Because be filled with inflammable and explosive High Pressure Hydrogen in the metallurgical electric arc furnace of hydrogen, if do not have forehearth, blowing out argon or nitrogen must displace wherein hydrogen and just can tap a blast furnace or slag tap when tapping a blast furnace, frequent blowing out efficiency will reduce greatly.Had forehearth, main stove just can long-time continuous running, and forehearth taps a blast furnace to slag tap and displaces wherein hydrogen with argon, just not only easy, and can not affect main stove and run, but key is the iron mouth reliably will closing main stove, and the metallurgical electric arc furnace pressure of hydrogen is high, exceeds more than 10 times, blast furnace.Not blowing out is reduced pressure, and ordinary method is difficult to tap cinder mouth to close, but really can not avoid.Therefore the present invention is that forehearth devises above-mentioned height insulation hydraulic ceramic ladle valve.The diameter at this mouth of a river should design enough large according to heat size, and heat insulation effect is enough good, is enough to ensure that iron melt cinder liquid flows out smoothly and can not solidify and open and close freely.

Fig. 9 illustrates, the metallurgical pre-reducing furnace of a kind of hydrogen, and this is a kind of " the metallurgical rotary kiln of hydrogen ":

" hydrogen metallurgical rotary kiln " is a kind of electric supplementary heating, highly reliable sealing closed pressure resistant >10Mpa, have the liner of resist melt ferric oxide bonding, the metallurgical rotary kiln of a kind of hydrogen; This kiln is made up of kiln hood 919, kiln body 920, kiln tail 921 and transmission system 912 4 major part; The shells 91,99 of kiln hood, kiln body, kiln tail etc. are by the Ultra-low carbon high-quality structural steel of anti-hydrogen embrittlement or low-carbon austenitic manufacture, and in shell, table is provided with the ceramic hollow ball mould material of nitrogen blowing or the thermal insulating warm-keeping layer 92,910 etc. of moldable making; Within the thermal insulating warm-keeping layer 92 of kiln body 920, be provided with carbon fiber and do heating element and with the overall coated resistive heating cylindrical component 94 made comprehensively of reaction sintering silicon nitride, whole shaft tubular an electric heating element divides three sections of formations, be interconnected, and can power up separately, temperature monitoring and the regulation and control of furnace temperature stove skin can being carried out respectively, maximum heating temperature 1600 DEG C, making in stove once occur that furnace charge ring formation can be melted discharge; It stretches out one section of box hat, its external diameter is identical with box hat, and process the annular groove of flexible sealing ring, the flexible sealing ring group 913 that in-built boron nitride ceramics fibre or silicon carbide ceramic fiber wear ring and flexible graphite sealing ring alternately form, and form precise rotation coupling pair with the annular section of kiln hood anti-stick liner 911, thus form high temperature anti-hydrogen leakage tightness system, the resistant to elevated temperatures tungsten through insulation processing of carbon fiber exothermic part, molybdenum to be extended out cylindrical shell as electrical conductor, be connected with copper slip ring 95,96 etc., copper slip ring and outer steel shell insulate, by carbon brush or use Ti3SiC ₂the slide block input electric power of ceramic layered manufacture; But when the selected iron ore concentrate pellet that the particle diameter adopting the market fine grinding selected Iron concentrate ore deposit of granularity <0.1mm to granulate to obtain is 5 ~ 20mm, when carrying out less than 700 ~ 1200 DEG C low temperature richness hydrogen fast restores, also can not establish above-mentioned electric supplementary heating device, but high temperature anti-hydrogen leakage tightness system still must remain unchanged; The innermost layer furnace lining of kiln hood, kiln body, kiln tail all makes the anti-stick liner 97,911 etc. of resist melt ferric oxide bonding with silicon nitride combined silicon carbide or Sailong and silicon carbide combined refractory material laying, lifting muscle 98 is established with afterbody in the middle part of its shaft, kiln height isothermal segment forms reducing, shrinking percentage 15 ~ 25%; The box hat of kiln hood and kiln body, kiln tail and kiln body, mutually location is supported through radial and axial refractory ceramics bearing 915,916, and also form precise rotation cooperation with cylindrical surface each other, and with silicon carbide ceramic fiber wear ring, flexible graphite sealing ring, teflon seal ring alternately composition low temperature combination sealing 914, and pipeline and stopping valve 917 are set between inside and outside low temperature seal ring group, carry out pressurized seal for the argon gas inputted higher than furnace pressure, and monitoring instrument is set; Kiln hood 919, kiln tail 921 are respectively equipped with the bolster 922,923 be used as at 1.5 ~ 5 ° of scope adjustment rotary kiln work inclination angles.Kiln hood is provided with high temperature hydrogen input aperture and sponge iron relief outlet, and kiln tail is provided with tail gas delivery port and material inlet, and is provided with spiral conveyer 918; The metallurgical rotary kiln of hydrogen adopt 8 ~ 12 less length-to-diameter ratio, rotating speed 0.5 ~ 5R/min is stepless adjustable.

Figure 10, Figure 11, Figure 12 illustrate SOEC high temperature electrolysis of steam groove:

" SOEC high temperature electrolysis of steam groove " is the basis forming " SOEC high temperature electrolysis of steam groove heap ".First with the SrCeO of Y or Yb doping ₃or SrZrO ₃high-temperature proton-conductor solid electrolyte, or, use Y ₂o ₃the ZrO of doping ₂high temperature oxygen ion conductor solid electrolyte is the large string tubular type electrolysis list pond that core manufactures super high power; Practical electrolyzer is formed again according to the multiple electrolysis list pond of hydrogen manufacturing scale; Finally with the extra heavy electrolyzer heap of multiple electrolyzer superposition compositions one, with the mass-producing of satisfied metallurgy and energy resource system; Proton conductor solid electrolyte electrolyzer is piled, and can go out anhydrous pure hydrogen by Direct Electrolysis, can simplify hydrogen metallurgical technology System's composition, energy-conservation, reduce costs, recommend as hydrogen metallurgical preferably electrolyzer heap; High temperature oxygen ion conductor solid electrolyte is applied more in a fuel cell, and material cost is lower, but the hydrogen that electrolysis produces contains a large amount of water vapour, refrigerated separation reheating just must can be applied to the prereduction of hydrogen metallurgy, recommend alternative;

The structure of described proton conductor solid electrolyte electrolysis list pond (Figure 11) is: with Zirconia reinforced alumina porous ceramics slurry, or prescind ceramic alumina fiber or Mullite Ceramic Fibres toughened aluminum oxide porous ceramics slurry, pore former is done with activity charcoal powder, extrusion moulding, then sintering makes void content>=50%, internal diameter is φ 30 ~ 100 ± 0.05mm, length is 1500 ~ 3000mm, wall thickness is 2 ~ 5mm, the macro porous ceramic support pipe 111 that one end is closed, the peripheral segmentation of supporting tube uses plasma spraying from inside to outside successively, or electrochemical vapor deposition etc. to manufacture segment length be 30 ~ 100mm, intersegmentally be spaced apart 2 ~ 5mm, thickness is the LaMnO of Ca or the Sr doping of 1 ~ 2mm ₃deng porous ceramics anode layer 117, thickness is the SrCeO of Y or the Yb doping of 0.1 ~ 1mm ₃or SrZrO ₃isopyknic proton conductor solid electrolyte layer 113, thickness be 1 ~ 2mm, Ni volume ratio 35 ~ 60% Ni-YSZ porous metalloceramic cathode layer 114 and with Ca, Sr, Co doping LaCrO ₃or YCO ₃pottery connects body 115 and is coupled together with the cathode layer 114 of the last period by the anode layer 117 of each section successively, but must not be communicated with to prevent short circuit with the cathode layer of a section subsequently, this dielectric substrate and linker also must carry out the scanning remelting sintering processes of even compact to improve its density with about 300 watts laser apparatus, supporting tube forward open end only makes the linker layer 112 be communicated with anode layer, and blind end only makes the linker layer 116 be communicated with cathode layer, the void content of cathode layer and anode layer all should>=50%,

The structure in described high temperature oxygen ion conductor solid electrolyte electrolysis list pond is substantially identical, and dissimilarity is that the ZrO2 oxygen ion conductor of the doping such as employing Y203, Yb203, Sc203, Sm203 makes solid electrolyte; Or manufacture its dielectric substrate with the LaGaO3 of Ca, Sr, Mg doping as solid electrolyte;

Described proton conductor solid electrolyte electrolyzer (Figure 10), adopt branched proton conductor solid electrolyte electrolysis list pond to be evenly assemblied in electrolysis list pond and yoke plate is held concurrently in anode collector plate 102 in annular array mode according to the scale of electrolytic hydrogen production, mutual pottery weldering carry out welding 120a with ensures sealing with or conduct electricity, this panel edges is provided with plate supply access point 117, electrolysis list pond inner chamber is inserted with the steam steam inject tube 103 prescinding ceramic alumina fiber or the manufacture of Mullite Ceramic Fibres reinforced alumina ceramic material, and be fixed on steam steam inject tube and on yoke plate 104, welding 120a is carried out in mutual pottery weldering, its external diameter and electrolysis list pond internal diameter form the annular gap of 0.5 ~ 1mm, and steam steam inject tube also forms anolyte compartment 120 between yoke plate and anode collector plate, this panel edges is provided with tail gas delivery port, cell body 107, anode collector plate 102, steam steam inject tube yoke plate 104 and electrolyzer base 105 through bolts assemblies together, are provided with the sealing member of low carbon stainless steel thin plate folder soft graphite ceramic fiber felt composite material each other, electrolyzer base 105 has high-temperature water vapor input aperture, with steam steam inject tube and yoke plate 104 forms steam distribution chamber, cell body 107 has hydrogen gas outlet and cathodic depolarization gas input aperture, depolarize gas is argon or hydrogen, and yoke plate is held concurrently, anode collector plate 102 forms cathode compartment with electrolysis list pond.Electrolyzer base and cell body are Ultra-low carbon high-quality structural steel or the low-carbon austenitic material of anti-hydrogen embrittlement, interior table scribble one deck 5 ~ 20mm thick prescind sapphire whisker reinforced alumina ceramic insulation heat preservation layer; The cathode collector plate frontside edge be made up of nickel cermet is provided with cathode connection point 110a, its internal surface is covered with one deck and the sizable nickel felt 109 of its surface-area, makes cathode collector plate form reliable flexible by nickel felt and each electrolysis list pool cathode end and conducts electricity and be connected;

Described high temperature oxygen ion conductor solid electrolyte electrolyzer (Figure 13), its structure is substantially identical with above-mentioned proton conductor solid electrolyte electrolyzer, and dissimilarity is: replace all proton conductor solid electrolyte electrolysis list ponds with high temperature oxygen ion conductor solid electrolyte electrolysis list pond; Cathodic depolarization gas input aperture in cell body transforms high-temperature steam input aperture into, hydrogen delivery port becomes hydrogen, steam mixing delivery port, steam steam inject tube tail gas delivery port on yoke plate becomes wet oxygen delivery port, high-temperature vapour input aperture on electrolyzer base transforms anode depolarize gas input aperture into, and depolarize gas is argon.

Novel material involved in the present invention all belongs to prior art, and all available existingly have ejusdem generis novel material and replaced.

Claims

1. a hydrogen metallurgy method, is characterized in that:

The fast basic technology circulation of (1) two step three:

The first step, with the metallurgical pre-reducing furnace of hydrogen to iron ore concentrate pellet, comprising the granulate particle diameter that obtains of 5 ~ 15mm iron essence lump ore pellet or Iron concentrate ore deposit, market is the Iron concentrate ore particle material of 5 ~ 20mm, carries out Fu Qing H ₂>=80%, high temperature 1200 ~ 1400 DEG C, high pressure 0.2 ~ 2MPa, quick prereduction, produces the sponge iron of reduction degree>=70%; The particle diameter adopting the market fine grinding selected Iron concentrate ore deposit of granularity <0.1mm to granulate to obtain is the selected iron ore concentrate pellet of 5 ~ 20mm, carries out Fu Qing H ₂>=90%, low temperature 700 ~ 1200 DEG C, high pressure 0.2 ~ 2MPa, quick prereduction, produces the sponge iron of reduction degree>=80%, all flows to hydrogen metallurgy smelting pyrolyzer to be incubated air-tight manner;

Second step, smelts pyrolyzer with hydrogen metallurgy, realizes Sweet natural gas or coal-seam gas, shale gas, underground gas maked coal, biogas, combustible ice gasification gas and brown coal perhydrous coal dry powder, plant drymeal, algae dry powder, is equipped with hydrogen or hydrocarbon fuel gas does carrier gas; Form jet by hydrogen metallurgy smelting pyrolyzer coreless armature and smelt pyrolyzer more than 3000 DEG C high temperature direct current plasma arc arc cores through hydrogen metallurgy, under high temperature condition, rapid cleavage is high temperature hydrogen and high temperature carbon black instantaneously; High temperature hydrogen is produced sponge iron with the metallurgical pre-reducing furnace of tail gas form output direct supply hydrogen for the quick prereduction of this stove rich, high temperature hydrogen and is provided hydrogen source; The carbon black that cracking simultaneously produces enters melting high temperature iron liquid melt pool and manufactures melting high temperature saturated carbon containing iron liquid; Flashmelt reduction and slag sluicing system is eventually carried out to the sponge iron of the metallurgical pre-reducing furnace input of hydrogen, produces molten iron or half steel; Thus complete the fast basic technology circulation continuous seepage of metallurgical two steps three of hydrogen;

(2) metallurgical waste heat high-temperature water vapour electrolytic hydrogen production: utilize hydrogen metallurgical pre-reducing furnace high temperature height enthalpy using waste heat from tail gas, produce 600 ~ 1000 DEG C of high-temperature vapors, again with proton conductor solid electrolyte high temperature electrolysis of steam groove heap, or oxygen ion conductor solid electrolyte high temperature electrolysis of steam groove heap, to produced high-temperature vapor, implement less energy-consumption high-temperature water and steam electrolytic hydrogen production; The pure hydrogen of high temperature wherein obtained by proton conductor solid electrolyte high temperature electrolysis of steam groove heap, directly feeds back to the metallurgical pre-reducing furnace of hydrogen, as the supplemental hydrogen source of producing sponge iron, the Sweet natural gas hydro carbons amount of consumed gas of molten iron per ton is reduced to 100m ³below; And the hydrogen obtained by piling with oxygen ion conductor solid electrolyte high temperature electrolysis of steam groove, containing a large amount of water vapour, need purify through exhaust treatment system refrigerated separation, and again be heated up by interchanger heat absorption, and then feed back to the metallurgical pre-reducing furnace of hydrogen, its by-product oxygen drying process recoverable;

(3) tail gas separation and CO transformation and hydrogen production: to producing the metallurgical pre-reducing furnace tail gas of hydrogen after water vapor cooling through heat exchange, proceed dedusting, heat exchange, bag filter, washing, desulfurization, CO conversion, gas delivery, reclaim hydrogen, carbonic acid gas, nanometer carbon black, argon and sulphur; By reclaimed technical pure hydrogen, the hydrogen cooling system of the metallurgical cracking smelting furnace of part feed-in hydrogen, but hydrogen-cooled and recovery of heat is carried out to the metallurgical cracking smelting furnace of hydrogen, part feed-in tail gas heat-exchange system carries out heat absorption and heats up, and then hot for two portions hydrogen is all fed back to the metallurgical pre-reducing furnace of hydrogen, the cold technical pure hydrogen of flap portion heats up directly output as the hydrogen energy source of hydrogen energy source automobile without the need to heat absorption; The argon reclaimed, then open for system device, stop, keep in repair, pressurized seal and hydrogen metallurgical cracking smelting furnace forehearth is when tapping a blast furnace and slag tap, drive away wherein air, and as the depolarize gas of solid electrolyte high-temperature water vapour electrolytic groove, recycle and reuse repeatedly;

Wherein hydrogen metallurgy smelts pyrolyzer, there is hydrogen-cooled body of heater (1), and hydrogen-cooled bell (3), between body of heater and bell and all outer Link Ports be equipped with the gasket (2) formed with the austenitic stainless steel leather wallet flexible graphite plate of anti-hydrogen embrittlement, hydrogen-cooled electrode insulation location current collection tightness system (5) is just directly installed on the central position of bell (3) by gasket, just arranged by gasket with prescinding branched ceramic feed-pipe (4) that boron nitride ceramics fibre or silicon carbide ceramic fiber reinforcement reaction sintering silicon nitride material make and to locate around current collection tightness system at hydrogen-cooled electrode insulation and stretch into burner hearth, hydrogen-cooled annular cylinder electrode lifting device (6) is just arranged on the upper surface of hydrogen-cooled electrode insulation location current collection tightness system (5) also with one heart by insulating mat, high strength coreless armature (7) with check valve joint is just arranged within hydrogen-cooled annular cylinder electrode lifting device, burner hearth core area is stretched in its lower end, and with hydrogen-cooled annular cylinder electrode lifting device (6) electrode be elevated arbitrarily and hover, the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and/or cinder notch (8) are arranged in cupola well slag line following molten pig liquid band, the ladle heel sheaf space preventing plasma arc burn furnace bottom is left apart from furnace bottom, before each blow-on, application argon or nitrogen flooding are removed out hydrogen metallurgy and are smelted all air in pyrolyzer, and smelt in pyrolyzer at hydrogen metallurgy the steel scrap scrap iron placed enough electric arc furnace starting the arc and its ladle heel sheaf space can be filled up after melting, put down electrode direct current arc again to be melted and produce melting high temperature iron liquid molten bath, the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and/or cinder notch (8) are through the forehearth (9) detecting displacement apparatus with gaseous constituent, operate from forehearth, forehearth (9) is put at the molten iron and slag of smelting iron layer top of checkmating under pyrolyzer melting continuously condition, the capacity smelting pyrolyzer according to hydrogen is different, arranges multiple iron mouth and forehearth, described hydrogen-cooled body of heater (1) and hydrogen-cooled bell (3) are double-deck high-quality Ultra-low carbon structure iron or low-carbon austenitic structure, Integral sealing compressive strength >5MPa, body of heater bell appearance is common aluminum silicate fiber spray coating heat preservation layer, furnace bottom section is divided in double-layer stainless steel interlayer, cupola well section, shaft section, bell section, volution is established to cool hydrogen channel in segmentation, the origin or beginning of passage and terminal weld inlet pipe (10) respectively, with escape pipe (13), each inlet pipe connects cooling hydrogen inlet manifold (12) by Electromagnetic Flow variable valve, each escape pipe is connected cooling hydrogen and to be given vent to anger house steward (14), all be embedded with thermopair in each section of furnace lining carry out detection and automatically control, its cooling intensity is, by furnace bottom, cupola well, the working temperature of the innermost layer refractory materials of slag line controls between 1000 ~ 1100 DEG C, impel inner lining surface to form thin layer slag iron and " freeze housing ", body of heater box hat internal surface is provided with the convex tendon keeping refractory materials and strengthen furnace wall, the furnace lining being close to box hat internal surface is prescind sapphire whisker or prescind the ceramic mould material that boron nitride fibre and silicon nitride or aluminum nitride powder be mixed, ramming mass, the high heat conductance height insulation furnace lining of moldable making, body of heater section, the liner of cupola well section contact molten iron and slag is the brick layer of mold pressing ultramicropore silicon nitride combined silicon carbide ceramic cup, furnace bottom section is provided with the conducting hearth copper plate electrode of drawing with the copper rod welding of flanged dish, 3 ~ 4 layers of mold pressing ultramicropore carbon brick are had on conducting hearth copper plate electrode, the superiors are laid on end mold pressing ultramicropore magnesia carbon brick, brickwork joint is less than 1mm, build by laying bricks or stones with high-quality carbonaceous clay,

Described high temperature electrolysis of steam groove heap, is characterized in that: first with the SrCeO of Y or Yb doping ₃or SrZrO ₃high-temperature proton-conductor solid electrolyte, or, use Y ₂o ₃the ZrO of doping ₂high temperature oxygen ion conductor solid electrolyte is the large string tubular type electrolysis list pond that core manufactures super high power; Practical electrolyzer is formed again according to the multiple electrolysis list pond of hydrogen manufacturing scale; Finally with the extra heavy electrolyzer heap of multiple electrolyzer superposition compositions one, with the mass-producing of satisfied metallurgy and energy resource system; Proton conductor solid electrolyte electrolyzer is piled, and can go out anhydrous pure hydrogen by Direct Electrolysis, simplify hydrogen metallurgical technology System's composition, energy-conservation, reduce costs;

The SrCeO of described Y or Yb doping ₃or SrZrO ₃high-temperature proton-conductor solid electrolyte to be the structure in large string tubular type electrolysis list pond that core manufactures super high power be: with Zirconia reinforced alumina porous ceramics slurry, or prescind sapphire whisker or mullite fiber toughened aluminum oxide porous ceramics slurry, extrusion moulding, then sintering makes void content>=50%, internal diameter is φ 30 ~ 100 ± 0.05mm, length is 1500 ~ 3000mm, wall thickness is 2 ~ 5mm, the macro porous ceramic support pipe (111) that one end is closed, the peripheral segmentation of supporting tube plasma spraying such as use grade successively from inside to outside, or electrochemical vapor deposition manufacture segment length is 30 ~ 100mm, intersegmentally be spaced apart 2 ~ 5mm, thickness is the LaMnO of Ca or the Sr doping of 1 ~ 2mm ₃porous ceramics anode layer (117), thickness is Y or the Yb doping SrCeO of 0.1 ~ 1mm ₃or SrZrO ₃fine and close proton conductor solid electrolyte layer (113), thickness be 1 ~ 2mm, Ni volume ratio 35 ~ 60% Ni-YSZ porous metalloceramic cathode layer (114) and with Ca, Sr, Co doping LaCrO ₃or YCO ₃pottery connects body (115) and the anode layer (117) of each section and the cathode layer (114) of the last period is coupled together successively, but must not be communicated with to prevent short circuit with the external cathode layer of a section subsequently, this dielectric substrate and linker also must carry out the scanning remelting sintering processes of even compact to improve its density with 300 watts of laser apparatus, supporting tube forward open end only makes the linker layer (112) be communicated with anode layer, and blind end only makes the linker layer (116) be communicated with cathode layer, the void content of cathode layer and anode layer all should>=50%,

Described Y ₂o ₃the ZrO of doping ₂high temperature oxygen ion conductor solid electrolyte is the large string tubular type electrolysis list pond that core manufactures super high power, adopts Y ₂o ₃, Yb ₂o ₃, Sc ₂o ₃, Sm ₂o ₃the ZrO of doping ₂oxygen ion conductor makes solid electrolyte; Or with Ca, Sr, Mg doping LaGaO ₃its dielectric substrate is manufactured as solid electrolyte;

The SrCeO of described Y or Yb doping ₃or SrZrO ₃high-temperature proton-conductor solid electrolyte be the practical electrolyzer that core manufactures the large string tubular type electrolysis list pond composition of super high power, adopt branched proton conductor solid electrolyte electrolysis list pond to be evenly assemblied in electrolysis list pond and yoke plate is held concurrently in anode collector plate (102) in annular array mode according to the scale of electrolytic hydrogen production, mutual pottery weldering is carried out welding (120a), this panel edges is provided with plate supply access point (110), electrolysis list pond inner chamber is inserted with the steam steam inject tube (103) prescinding the manufacture of sapphire whisker reinforced alumina ceramic material, and be fixed on steam steam inject tube and on yoke plate (104), mutual pottery weldering is carried out welding (120a), its external diameter and electrolysis list pond internal diameter form the annular gap of 0.5 ~ 1mm, and steam steam inject tube also forms anolyte compartment (120) between yoke plate and anode collector plate, this panel edges is provided with tail gas delivery port, cell body (107), anode collector plate (102), steam steam inject tube yoke plate (104) and electrolyzer base (105) through bolts assemblies together, are provided with the sealing member of low carbon stainless steel thin plate folder soft graphite ceramic fiber felt composite material each other, (105) have high-temperature water vapor input aperture to electrolyzer base, with steam steam inject tube and yoke plate (104) forms steam distribution chamber, cell body (107) has hydrogen gas outlet and cathodic depolarization gas input aperture, depolarize gas is argon or hydrogen, and yoke plate is held concurrently, anode collector plate (102) forms cathode compartment with electrolysis list pond,

Electrolyzer base and cell body are Ultra-low carbon high-quality structural steel or the low-carbon austenitic material of anti-hydrogen embrittlement, interior table scribble one deck 5 ~ 20mm thick prescind sapphire whisker reinforced alumina ceramic insulation heat preservation layer; Cathode collector plate (100) edge be made up of nickel cermet is provided with cathode connection point (110a), its internal surface is covered with one deck and the sizable nickel felt (109) of its surface-area, makes cathode collector plate form reliable flexible by nickel felt and each electrolysis list pool cathode end and conducts electricity and be connected;

Described Y ₂o ₃the ZrO of doping ₂high temperature oxygen ion conductor solid electrolyte is the practical electrolyzer that core manufactures the large string tubular type electrolysis list pond composition of super high power, its structure is substantially identical with above-mentioned proton conductor solid electrolyte electrolyzer, and dissimilarity is: replace all proton conductor solid electrolyte electrolysis list ponds with high temperature oxygen ion conductor solid electrolyte electrolysis list pond; Cathodic depolarization gas input aperture in cell body transforms high-temperature steam input aperture into, hydrogen delivery port becomes hydrogen, steam mixing delivery port, steam steam inject tube tail gas delivery port on yoke plate becomes wet oxygen delivery port, high-temperature vapour input aperture on electrolyzer base transforms anode depolarize gas input aperture into, and depolarize gas is argon.

2. hydrogen metallurgy method according to claim 1, is characterized in that: in the fast basic technology circulation of described two steps three, second step is, desulfurization dewatering Sweet natural gas, coal-seam gas, underground gas maked coal, shale gas, biogas, combustible ice gasification gas hydrocarbon fuel gas is adopted to carry out the hydrogen manufacturing of plasma rapid cleavage, by molten iron 0 ~ 200m per ton ³sweet natural gas or the suitable various hydrocarbon fuel gas of hydrogen content, the central duct of cracking furnace zone check valve high strength coreless armature is smelted by hydrogen metallurgy, with 1 ~ 6m/s jet, through the smelting direct current plasma electric arc arc core of temperature more than 3000 DEG C of powerful, more than 1300 DEG C are just heated to the moment of 0.5 ~ 4 millisecond, under high temperature condition, hydrocarbon fuel gas will be all high temperature hydrogen and nanometer carbon black by rapid cleavage, the trace amounts of CO existed in combustion gas ₂also will be reduced to CO by high-temperature nano carbon black, scission reaction time <0.5ms, average reaction temperature 1300 ~ 1600 DEG C, reaction pressure 0.2 ~ 2Mpa, lower pressure is conducive to scission reaction, cracking energy consumption 3 ~ 4MJ/Nm ³, hydrogen metallurgy is smelted pyrolyzer and is mainly adopted unlimited molten bath standard or the operation of submerged-arc smelting standard, the carbon black that cracking produces is at jet mass force, under Arc effect, at high temperature foam slag, slag, sponge iron shroud covering under, directly enter in the melting high temperature iron liquid below coreless armature, become the dissolved carbon in melting high temperature iron liquid, thus produce sponge iron Flashmelt and reduce necessary high-temperature fusion saturated carbon containing iron liquid, directly to be fallen into from the high-temperature sponge iron of the metallurgical pre-reducing furnace input of hydrogen by the hydrogen metallurgy one or more filling tubes smelted pyrolyzer bell or this melting high temperature saturated carbon containing iron liquid is progressively fused in branch layering, realize Flashmelt reduction slag sluicing system immediately and smelt molten iron discharging or half steel, realize the less energy-consumption Flashmelt reduction metallurgical process of sponge iron, combustion gas cracking hydrogen metallurgy adopts the sponge iron of reduction degree >90%, the CO<50kg that melting and reducing ton iron produces, the small part of the hydrogen that cracking produces participates in the reduction reaction of non-reducing iron oxides in sponge iron, the overwhelming majority smelts pyrolyzer tail gas relief outlet and the direct mode of communicating of metallurgical pre-reducing furnace reducing gas input aperture two stove of hydrogen with high-temperature tail gas form and hydrogen metallurgy, directly flow to the metallurgical pre-reducing furnace of hydrogen, fast restore produces sponge iron, thus realizes hydrogen metallurgical technology circulation continuous seepage,

When reduction degree>=80% of sponge iron, ton iron Sweet natural gas add-on <170m ³time, the hydrogen manufacturing of metallurgical waste heat high temperature electrolysis of steam need be implemented, to supplement the insufficient section splitting combustion gas solution hydrogen; When enforcement ground water power, wind-powered electricity generation, nuclear power aboundresources, then utilize whole hydrogen metallurgical waste heat high-temperature vapor to carry out electrolytic hydrogen production, also institute's hydrogen manufacturing stored in the peak and low valley phase and utilize with post-equalization, institute's hydrogen manufacturing is enough to Sweet natural gas hydro carbons gas consumption to reduce to 100m ³below/t molten iron, but for zero time still need to add 30 ~ 70kg/t pure carbon powder replace carbon in Sweet natural gas to meet the carbon needed for carburizing sponge iron, sponge iron melting and reducing and molten iron carburizing;

When the reduction degree of sponge iron is 70 ~ 80%, Sweet natural gas add-on>=170m ³during/t, need not implement residual heat high-temperature water vapour electrolytic hydrogen production, the cracking of simple dependence Sweet natural gas hydrocarbon fuel gas can realize hydrogen metallurgy, and this is suitable for the area that the resourceful area of Sweet natural gas hydrocarbon fuel gas or water power, wind-powered electricity generation, nuclear power resource are comparatively tight or its price is higher.

3. hydrogen metallurgy method according to claim 1, is characterized in that: in the fast basic technology circulation of described two steps three, second step is: adopt brown coal perhydrous coal dry powder and plant drymeal as the raw material of cracking hydrogen production, when adopting brown coal perhydrous coal dry powder, hydrogen content>=4%, ash <2%, sulphur phosphorus content <0.2% need be adopted, moisture content <1%, the fine purifiation of granularity <0.1mm selects drying to mill brown coal perhydrous coal dry powder, and its amount of allocating into is molten iron 50 ~ 150kg per ton, when adopting plant drymeal to make hydrogen feedstock, desliming roots of plants cauline leaf need be shredded, and through 200 ~ 300 DEG C of high temperature drying dehydrations, mill and become the dry powder of granularity <0.1mm, its amount of allocating into is molten iron 100 ~ 250kg per ton, and every kilogram of dry powder need join 1 ~ 3Nm ³hydrogen or hydrocarbon fuel gas do carrier gas, the central duct of cracking furnace zone check valve high strength coreless armature is smelted by hydrogen metallurgy, with 1 ~ 6m/s jet, through the smelting direct current plasma electric arc arc core of temperature more than 3000 DEG C of powerful, under smelting pyrolyzer high temperature condition, brown coal perhydrous coal dry powder, plant drymeal will be all hydrogen, hydrocarbon gas, carbon black, charred ashes, CO, CO by rapid cleavage ₂, the very complicated composition of N, water vapor, wherein hydrocarbon gas extremely unstable under hot conditions more than 1300 DEG C, is decomposed into hydrogen and carbon black, CO by continuing ₂also CO will be reduced to by high temperature carbon black, carbon black, charred ashes is at jet mass force, under Arc effect, at high temperature foam slag, slag, sponge iron shroud covering under, directly enter in the melting high temperature iron liquid below coreless armature, become the dissolved carbon in melting high temperature iron liquid, thus produce sponge iron Flashmelt and reduce necessary high-temperature fusion saturated carbon containing iron liquid, directly to be fallen into from the high-temperature sponge iron of the metallurgical pre-reducing furnace input of hydrogen by the hydrogen metallurgy one or more filling tubes smelted pyrolyzer bell or this melting high temperature saturated carbon containing iron liquid is progressively fused in branch layering, realize Flashmelt reduction slag sluicing system immediately and smelt molten iron discharging or half steel, realize the less energy-consumption Flashmelt reduction metallurgical process of sponge iron, the small part of the hydrogen that cracking produces participates in the reduction reaction of non-reducing iron oxides in sponge iron, the overwhelming majority smelts pyrolyzer tail gas relief outlet and the direct mode of communicating of metallurgical pre-reducing furnace reducing gas input aperture two stove of hydrogen with high-temperature tail gas form and hydrogen metallurgy, directly flow to the metallurgical pre-reducing furnace of hydrogen, fast restore produces sponge iron, thus realizes hydrogen metallurgical technology circulation continuous seepage.

4. the metallurgy of the hydrogen for hydrogen metallurgy method smelts pyrolyzer, it is characterized in that: there is hydrogen-cooled body of heater (1), and hydrogen-cooled bell (3), between body of heater and bell and all outer Link Ports be equipped with the gasket (2) formed with the austenitic stainless steel leather wallet flexible graphite plate of anti-hydrogen embrittlement, hydrogen-cooled electrode insulation location current collection tightness system (5) is just directly installed on the central position of bell (3) by gasket, just arranged by gasket with prescinding branched ceramic feed-pipe (4) that boron nitride ceramics fibre or silicon carbide ceramic fiber reinforcement reaction sintering silicon nitride material make and to locate around current collection tightness system at hydrogen-cooled electrode insulation and stretch into burner hearth, hydrogen-cooled annular cylinder electrode lifting device (6) is just arranged on the upper surface of hydrogen-cooled electrode insulation location current collection tightness system (5) also with one heart by insulating mat, high strength coreless armature (7) with check valve joint is just arranged within hydrogen-cooled annular cylinder electrode lifting device, burner hearth core area is stretched in its lower end, and with hydrogen-cooled annular cylinder electrode lifting device (6) electrode be elevated arbitrarily and hover, the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and/or cinder notch (8) are arranged in cupola well slag line following molten pig liquid band, the ladle heel sheaf space preventing plasma arc burn furnace bottom is left apart from furnace bottom, before each blow-on, application argon or nitrogen flooding are removed out hydrogen metallurgy and are smelted all air in pyrolyzer, and smelt in pyrolyzer at hydrogen metallurgy the steel scrap scrap iron placed enough electric arc furnace starting the arc and its ladle heel sheaf space can be filled up after melting, put down electrode direct current arc again to be melted and produce melting high temperature iron liquid molten bath, the high heat preserving ceramic hydraulic efficiency slide valve formula mouth of a river and/or cinder notch (8) are through the forehearth (9) detecting displacement apparatus with gaseous constituent, operate from forehearth, forehearth (9) is put at the molten iron and slag of smelting iron layer top of checkmating under pyrolyzer melting continuously condition, the capacity smelting pyrolyzer according to hydrogen is different, arranges multiple iron mouth and forehearth, described hydrogen-cooled body of heater (1) and hydrogen-cooled bell (3) are double-deck high-quality Ultra-low carbon structure iron or low-carbon austenitic structure, Integral sealing compressive strength >5MPa, body of heater bell appearance is common aluminum silicate fiber spray coating heat preservation layer, furnace bottom section is divided in double-layer stainless steel interlayer, cupola well section, shaft section, bell section, volution is established to cool hydrogen channel in segmentation, the origin or beginning of passage and terminal weld inlet pipe (10) respectively, with escape pipe (13), each inlet pipe connects cooling hydrogen inlet manifold (12) by Electromagnetic Flow variable valve, each escape pipe is connected cooling hydrogen and to be given vent to anger house steward (14), all be embedded with thermopair in each section of furnace lining carry out detection and automatically control, its cooling intensity is, by furnace bottom, cupola well, the working temperature of the innermost layer refractory materials of slag line controls between 1000 ~ 1100 DEG C, impel inner lining surface to form thin layer slag iron and " freeze housing ", body of heater box hat internal surface is provided with the convex tendon keeping refractory materials and strengthen furnace wall, the furnace lining being close to box hat internal surface is prescind sapphire whisker or prescind the ceramic mould material that boron nitride fibre and silicon nitride or aluminum nitride powder be mixed, ramming mass, the high heat conductance height insulation furnace lining of moldable making, body of heater section, the liner of cupola well section contact molten iron and slag is the brick layer of mold pressing ultramicropore silicon nitride combined silicon carbide ceramic cup, furnace bottom section is provided with the conducting hearth copper plate electrode of drawing with the copper rod welding of flanged dish, 3 ~ 4 layers of mold pressing ultramicropore carbon brick are had on conducting hearth copper plate electrode, the superiors are laid on end mold pressing ultramicropore magnesia carbon brick, brickwork joint is less than 1mm, build by laying bricks or stones with high-quality carbonaceous clay,

Described high strength coreless armature (7) is with high strength isostatic pressed impregnated graphite or Ti ₃siC ₂ceramic layered manufacture, and process through precision optical machinery, diameter need smelt pyrolyzer capacity according to hydrogen and the calculating of electrode working current size is determined, Single lead length is 2 ~ 4m, whole electrode is according to electric furnace size, propping up electrode series winding by some lists to form, realizing series winding by being with the electrode contact body (44) of check valve, the structure of this electrode contact is: spool (45) is placed in jointing body (44) inner chamber actively, rely on the non-magnetic stainless steel spring (46) on spring support (47) to be resisted against spool rear portion, make spool shutoff on the opening of fittings body front portion, be be threaded between spring support (47) with fittings body (44), adjustment spring pressure, its fittings body, spool, spring support all manufactures with described electrode same material, between fittings body (44) and electrode (41) and between electrode end surface, be provided with soft graphite O-ring seals (42, 43), after Electrode connection is got up, stove inner high voltage hydrogen is unlikely leaks, and to be convenient to after consumption of electrode shortens spreading in addition immediately, during spreading, before fully tightening electrode, application argon gas displaces the air in this extension electrode endoporus, normal work is entered after fully tightening again.

5. hydrogen metallurgy as claimed in claim 4 smelts pyrolyzer, and wherein said check valve makes separately and is arranged under hollow connector.

6. hydrogen metallurgy smelts pyrolyzer according to claim 4, it is characterized in that: hydrogen metallurgy smelts hydrogen-cooled electrode insulation location current collection tightness system (5) of pyrolyzer, there is the insulation retaining ring body (51) prescinding boron nitride or the making of silicon carbide fiber reinforcement reaction sintering silicon nitride, and with fine copper or pure nickel or nickel cermet, the ring header body (53) made, therebetween after assembling, form the hydrogen-cooled electrode insulation location current collection tightness system annular solid of a unification, its Inner Constitution cooling hydrogen circulation passage, and on the bonding surface of the two, be provided with the O shape flexible graphite sealing ring (54 preventing cooling hydrogen from leaking, 510), between insulation retaining ring body (51) inner ring surface and high strength coreless armature, the wear ring string (52 that boron nitride ceramics fibre wear ring and flexible graphite sealing ring constitute jointly is respectively equipped with between outer ring surface and bell, 55), ring header body (53) is provided with soft graphite current collection wear ring string (56) with the bonding surface place of coreless armature (7) and compresses with non-magnetic stainless steel swivel nut (57), sealing ring string is except sealing function, prior effect is conduction and heat conduction, therefore the quantity of soft graphite current collection wear ring should be determined according to the working current size of plasma arc and heat calculation, guarantee that there is enough conductive section sum heat-conducting areas, ring header body (53) is also provided with joint (58) that the cooling joint (59) that enters of hydrogen and cooling hydrogen exports and direct current negative pole connects electric pile crown (510).

7. hydrogen metallurgy smelts pyrolyzer according to claim 4, it is characterized in that: hydrogen metallurgy smelts the hydrogen-cooled annular cylinder electrode lifting device of pyrolyzer, the upper band-type brake (613) identical by structure and lower band-type brake (614) and hoist cylinder (610) form; Upper and lower band-type brake (613,614) structure: swing that oil motor (62) is arranged on that band-type brake body (61) is upper, the axle that swings oil motor (62) is connected with screw rod (63) with feather key, screw end head is resisted against on the axle for holding tightly on the brake shoe block (64) of coreless armature (7) and is fixedly connected with a screw rod (63), and screw rod outer end is resisted against the brake shoe block (64) for holding coreless armature (7) tightly; The inner ring (65) of hoist cylinder (610) is 3 layers of hydrogen-cooled structure, inside is provided with cooling hydrogen circulation passage, connect firmly with the band-type brake body (61) of lower band-type brake, and constitute jointly annular cylinder with outer shroud (611), the annular piston of oil cylinder and annular piston bar (69) and sealing member thereof are just mounted in it, and the band-type brake body that piston rod stretches out cylinder body and upper band-type brake (613) connects firmly; The inner ring cylinder body of hoist cylinder (610) is provided with and cools cooling hydrogen air inlet that hydrogen channel is communicated with, air outlet adapter (66,67), outer shroud is provided with hydraulic liquid turnover joint (68,612), all steel annular parts of oil cylinder, all use non-magnetic stainless steel manufacture, oil cylinder anti-flame hydraulic fluid drives.

8. hydrogen metallurgy smelts pyrolyzer according to claim 4, it is characterized in that: described hydrogen metallurgy smelts the ladle valve of pyrolyzer, is that the large parts series winding of hydraulic ram (78) three driven by ceramic slide body (76), heat-proof device (77), anti-flame hydraulic fluid is formed; Pottery slide body, uses boron nitride fiber reinforced reactively sintered silicon nitride ceramics manufacture by spool (71) again, and with plasma spraying boron nitride antifriction layer; Internal spool valve cover (72) is also manufactured by boron nitride fiber reinforced reactively sintered silicon nitride ceramics; Be snug sliding fit between spool and internal spool valve overlap, have flexible graphite sealing ring (73) to seal furnace gas; Moderate soak layer (74) is the ceramic mould material manufacture made from the silicon carbide granular refractory fiber of lower thermal conductivity or nitrogen blowing alumina hollow ball and silicon nitride combined silicon carbide powder, outer installation sleeve (75) is manufactured, with mounting flange by sapphire whisker intensified response sintered silicon nitride ceramic material; The duct that molten iron flows out is opened at middle part after valve pocket, thermal insulation layer, the combination of outer installation sleeve, and opened and closed by spool, the body of rod of spool (71) stretches in heat-proof device (77), is connected with the piston rod of hydraulic ram (78);

Described have gaseous constituent and detect displacement apparatus and the forehearth (9) of slag-tapping function of independently tapping a blast furnace, and this forehearth is made up of body of heater (81), bell (83) and Thin Stainless Steel plate holder flexible graphite sealing pad (82) be clipped between both bonding surface; Insulation ruhmkorff coil (813) is set outside body of heater, lower portion of furnace body be provided with common iron mouth and or cinder notch (812), be fixedly connected with main stove with web plate (810) by flange (811), by ladle valve from main stove input iron liquid and/or slag liquid, and closed at any time as required or open, between forehearth and main stove, a horizontal height is also separately established to be incubated hydraulic ceramic guiding valve, to change spool and the valve pocket of " high insulation hydraulic ceramic ladle valve and/or cinder notch "; Bell is provided with hydrogen content detecting sensor (84), pressure, temperature and remote control display and control instrument (89), and be provided with hydrogen delivery valve (85), air diffusion valve (86), spark arrester (87), bleeder (88); Lower portion of furnace body is provided with argon gas input tube (814), stopping valve and porous plug.

9. for the metallurgical pre-reducing furnace of hydrogen of hydrogen metallurgy method described in any one of claim 1-3, it is characterized in that: the metallurgical pre-reducing furnace of hydrogen is a kind of electric supplementary heating, highly reliable sealing closed pressure resistant >10Mpa, have the metallurgical rotary kiln of a kind of hydrogen of the liner of resist melt ferric oxide bonding, this kiln is made up of kiln hood (919), kiln body (920), kiln tail (921) and transmission system (912) four major part, the shell (91,99) of kiln hood, kiln body, kiln tail is by the Ultra-low carbon high-quality structural steel of anti-hydrogen embrittlement or low-carbon austenitic manufacture, and in shell, table is provided with the ceramic hollow ball mould material of nitrogen blowing or the thermal insulating warm-keeping layer (92,910) of moldable making, within the thermal insulating warm-keeping layer (92) of kiln body (920), be provided with carbon fiber and do heating element and with the overall coated resistive heating cylindrical component (94) made comprehensively of reaction sintering silicon nitride, whole shaft tubular an electric heating element divides three sections of formations, be interconnected, and power up separately, carrying out temperature monitoring and the regulation and control of furnace temperature stove skin respectively, maximum heating temperature 1600 DEG C, making in stove once occur that furnace charge ring formation is melted discharge, it stretches out one section of box hat, its external diameter is identical with box hat, and process the annular groove of flexible sealing ring, the flexible sealing ring group (913) that in-built boron nitride ceramics fibre or silicon carbide ceramic fiber wear ring and flexible graphite sealing ring alternately form, and form precise rotation coupling pair with the annular section of kiln hood anti-stick liner (911), thus form high temperature anti-hydrogen leakage tightness system, the resistant to elevated temperatures tungsten through insulation processing of carbon fiber exothermic part, molybdenum to be extended out cylindrical shell as electrical conductor, with copper slip ring (95, 96) be connected, copper slip ring and outer steel shell insulate, by carbon brush or use Ti ₃siC ₂the slide block input electric power of ceramic layered manufacture, but when the selected iron ore concentrate pellet that the particle diameter adopting the market fine grinding selected Iron concentrate ore deposit of granularity <0.1mm to granulate to obtain is 5 ~ 20mm, when carrying out 700 ~ 1200 DEG C of low temperature richness hydrogen fast restores, do not establish above-mentioned electric supplementary heating device, but high temperature anti-hydrogen leakage tightness system still must remain unchanged, the innermost layer furnace lining of kiln hood, kiln body, kiln tail all builds the anti-stick liner (97,911) making resist melt ferric oxide bonding by laying bricks or stones with silicon nitride combined silicon carbide, lifting muscle (98) is established with afterbody in the middle part of its shaft, kiln height isothermal segment forms reducing, shrinking percentage 0 ~ 25%, the box hat of kiln hood and kiln body, kiln tail and kiln body, mutually location is supported through radial and axial refractory ceramics bearing (915,916), and also form precise rotation cooperation with cylindrical surface each other, and with silicon carbide ceramic fiber wear ring, flexible graphite sealing ring, teflon seal ring alternately composition low temperature combination sealing (914), and pipeline and stopping valve (917) are set between inside and outside low temperature seal ring group, carry out pressurized seal for the argon gas inputted higher than furnace pressure, and monitoring instrument is set, kiln hood (919), kiln tail (921) are respectively equipped with the bolster (922,923) be used as at 1.5 ~ 5 ° of scope adjustment rotary kiln work inclination angles, kiln hood is provided with high temperature hydrogen input aperture and sponge iron relief outlet, and kiln tail is provided with tail gas delivery port and material inlet, and is provided with spiral conveyer (918), the metallurgical rotary kiln of hydrogen adopt 8 ~ 12 less length-to-diameter ratio, rotating speed 0.5 ~ 5R/min is stepless adjustable.