CN106041108A - Nickel-iron alloy dry granulation and methane steam reforming waste heat recovery device and method - Google Patents

Nickel-iron alloy dry granulation and methane steam reforming waste heat recovery device and method Download PDF

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CN106041108A
CN106041108A CN201610381128.6A CN201610381128A CN106041108A CN 106041108 A CN106041108 A CN 106041108A CN 201610381128 A CN201610381128 A CN 201610381128A CN 106041108 A CN106041108 A CN 106041108A
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methane
dilval
dry granulation
reforming reaction
reaction bed
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CN106041108B (en
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吕学伟
邱杰
张颖异
吕学明
王伦伟
贺文超
党杰
白晨光
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Chongqing University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/004—Systems for reclaiming waste heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a nickel-iron alloy dry granulation and methane steam reforming waste heat recovery device and method. According to the nickel-iron alloy dry granulation and methane steam reforming waste heat recovery device, the structure is simple; production, implementation, using and operation are all easy and convenient; the nickel-iron alloy dry granulation and methane steam reforming waste heat recovery method is combined; the nickel-iron alloy refining granulation effect is better ensured by adopting the dry granulation method; meanwhile, nickel-iron alloy waste heat can further be converted into resources required by methane steam reforming reaction in a multistage recovery mode that a physical method is combined with a chemical method; increasing of the nickel-iron alloy waste heat resource recovery utilization rate can be facilitated, so that the problems that the stainless steel smelting process requirements are difficult to meet by molten nickel-iron alloy granulation processing, and the waste heat resource recovery utilization rate of molten nickel-iron alloy granulation processing is low in the prior art are effectively solved; and the nickel-iron alloy dry granulation and methane steam reforming waste heat recovery device and method have very good industrial application value and can be applied and popularized in domestic metallurgical enterprises.

Description

Dilval dry granulation and methane vapor reforming waste-heat recovery device and method
Technical field
The present invention relates to metallurgical engineering, environmental protection and energy saving field, relate generally to the energy-saving and emission-reduction of metallurgical process, metallurgical cinder Dry granulation, particularly to a kind of dilval dry granulation and methane vapor reforming waste-heat recovery device and method.
Background technology
Rustless steel needs in producing to add ferronickel raw material, and granule when ferronickel enters stove is the least, more can shorten the smelting of steel-making The refining time, but simultaneously in order to ensure that ferronickel granule can pass through surface slag blanket, i.e. require that its quality can not be the least, thus ferronickel The granule of alloy can not be the least, and usual particle diameter is optimal at 10 ~ 40mm.At present, in ferronickel metallurgical technology, domestic whether Blast Furnace Method, blast furnace process or rotary kiln prereduction-electric furnace smelting process, on subsequent melt ferronickel water processes, mostly use biography Pig machine ingot casting+Mechanical Crushing the method for system.The smelting enterprise little to ferronickel yield, ferronickel grade is low, uses pig machine ingot casting Method, manufacturing condition can substantially meet requirement.But for high-grade nickel ferroalloy (nickel content is more than 25%), due to molten Point is high, and silicon, carbon content are relatively low, poor fluidity, can cause mold consume big, stripping result is poor, the equipment cleaning residual ferrum time is long, from And cause cast iron cycle period long, it is difficult to meet the demand that extensive ferronickel produces；Simultaneously as nickel is of high grade, ferronickel rigidity By force, ingot casting burr is difficult to clear up, and product appearance physical quality is poor, and yield rate and the cast iron response rate are the lowest；The ferronickel finally obtained Crumb size is the biggest, and its particle diameter, typically in the range of 150 ~ 200 millimeters, needs further grinding and processing ability preferably Meeting stainless steel-making process requirement, this adds grinding and processing cost and stainless steel smelting cost undoubtedly.
Additionally, due to the tapping temperature of dilval higher (usually 1600 ~ 1650 DEG C), use " pig machine ingot casting+ Mechanical Crushing " method obtain dilval block during, typically directly come by the way of water-spraying control to ferronickel close Ingot mould is lowered the temperature, and the most not only needs to consume substantial amounts of new water resource, is also easy to produce hydrogen at dilval in Cooling Process The explosion hazard gases such as gas, are easily mingled with impurity, easily cause transmission pipeline fouling and clogging in the hot water simultaneously obtained after water-cooled, these frauds End all limits the steam of its gained, hot water directly applies to heating, causes the water-cooled waste heat of melted dilval to be difficult to pass through The form of heating is recycled.Also there are some waste heat recovery schemes, reclaim melted dilval water-cooled institute by heat exchanger Obtain steam, the waste heat of hot water is used for generating electricity, but the efficiency utilization rate of its cogeneration is generally only capable of and reaches 20 ~ 25%, waste heat Resource utilization is low.
Therefore, in prior art, the granulation difficult processing of melted dilval is wanted directly to meet stainless steel-making process Ask and problem that its residual heat resources recovery utilization rate is low, need one in industry badly and can either preferably realize melted dilval Granulation, can possess again the Technology of higher residual heat resources recovery utilization rate.
Summary of the invention
For above-mentioned deficiency present in prior art, it is an object of the invention to provide a kind of dilval dry granulation And methane vapor reforming waste-heat recovery device, it is while realizing the granulation processing of liquid molten dilval, moreover it is possible to The in addition multistage recovery of enough waste heats to state dilval is converted into the resource requirement of methane-steam reforming, it is possible to help to carry The high recovery utilization rate to dilval residual heat resources, in order to solve in prior art the granulation difficult processing of melted dilval with Meet stainless steel-making process requirement and the low problem of its residual heat resources recovery utilization rate.
For achieving the above object, present invention employs following technical scheme:
A kind of dilval dry granulation and methane vapor reforming waste-heat recovery device, including dry granulation device, reforming reaction Bed, slag particle catcher, water circulating and evaporating condenser, water recycle heat exchanger and methane separation device；
The top of described dry granulation device is provided with dilval liquid entrance and gas outlet, and the middle part in dry granulation device is positioned at nickel Centrifugal granulation device, the bottom of dry granulation device and described reforming reaction bed it is provided with at the position directly below of ferroalloy liquid entrance Top connects connection；The bottom of reforming reaction bed is provided with funnelform discharging opening, and the bottom of reforming reaction bed is near funnel The sidewall of shape discharging opening position is provided with methane vapor air inlet；Described slag particle catcher is just to being arranged at reforming reaction bed Discharging opening below unloading position at, described water circulating and evaporating condenser be arranged at slag particle catcher bottom and can be with slag Carry out conduction of heat between grain catcher, and the steam outlet of water circulating and evaporating condenser is communicated to the methane water of reforming reaction bed Steam air inlet；
The gas outlet at described dry granulation device top is communicated to by being disposed with the gas channel of air exhauster and cleaner unit The air-flow heat exchanger channels entrance of water recycle heat exchanger, is driven air-flow to flow to the exchange of water cycling hot from dry granulation device by air exhauster The air-flow heat exchanger channels of device；The air-flow heat exchanger channels outlet of described water recycle heat exchanger is to the air inlet of methane separation device Mouthful, and the recirculated water heat exchange steam (vapor) outlet of water recycle heat exchanger is communicated to the methane vapor air inlet of reforming reaction bed；Institute State methane separation device for isolating methane from the gas entered, and by the methane of isolated and mixed tail gas respectively from it Methane gas outlet and mixed tail gas outlet are discharged, and the methane gas outlet of methane separation device is also communicated to reforming reaction bed Methane vapor air inlet.
In above-mentioned dilval dry granulation and methane vapor reforming waste-heat recovery device, as improvement project, institute State rotary drive motor that the centrifugal granulation device in dry granulation device arranges straight up by drive shaft and be arranged on rotation Drive the porous in the drive shaft of motor to be centrifuged revolving cup to constitute；Described porous be centrifuged revolving cup have at the bottom of one horizontally disposed glass and The wall of cup extended straight up along cup feather edge, porous is centrifuged the opening up of revolving cup and is right against the ferronickel conjunction of dry granulation device Gold liquid entrance, porous is centrifuged on the wall of cup of revolving cup circumferentially arranged with being arranged into the logical of several rows from bottom to top from position at the bottom of cup Hole, the thickness of described wall of cup is 5 ~ 10mm, and the aperture of described through hole is 10 ~ 20mm, is arranged in adjacent two through holes of same a line Spacing between edge is 5 ~ 10mm, and the spacing being arranged between adjacent two through hole edges of adjacent rows is 6 ~ 15mm, and The through hole of every adjacent rows is staggered.
In above-mentioned dilval dry granulation and methane vapor reforming waste-heat recovery device, as improvement project, institute State steam in water recycle heat exchanger is additionally operable to collect its air-flow heat exchanger channels and cool down the condensed water condensed and by condensation Water output is discharged, and the recirculated water water leg phase of the condensed water delivery outlet of water recycle heat exchanger and water circulating and evaporating condenser Connection.
In above-mentioned dilval dry granulation and methane vapor reforming waste-heat recovery device, preferably, institute Stating reforming reaction bed is moving bed or fluid bed.
In above-mentioned dilval dry granulation and methane vapor reforming waste-heat recovery device, preferably, institute State methane separation device and use stage variable pressure adsorption tower.
In above-mentioned dilval dry granulation and methane vapor reforming waste-heat recovery device, as improvement project, institute State and be provided with plate feed between the discharging opening of reforming reaction bed and slag particle catcher, in order to carry out the discharging opening of reforming reaction bed Feeding to slag particle catcher.
Accordingly, present invention also offers dilval dry granulation and methane vapor reforming exhaust heat recovering method；For This, present invention employs following technical scheme:
A kind of dilval dry granulation and methane vapor reforming exhaust heat recovering method, use above-mentioned dilval dry method grain Change and methane vapor reforming waste-heat recovery device implemented as follows:
1) startup optimization dilval dry granulation and methane vapor reforming waste-heat recovery device, controls in its dry granulation device Centrifugal granulation device rotary speed is 100 ~ 300rpm, and is passed through methane water in reforming reaction bed by its methane vapor air inlet Steam, in being driven dilval dry granulation and methane vapor reforming waste-heat recovery device by the air exhauster on gas channel Circulation of air flow；
2) the liquid molten dilval by 1600 ~ 1650 DEG C injects the dilval liquid entrance at dry granulation device top, flows into Centrifugal granulation device in dry granulation device, is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and in-flight Dilval molten drop carry out heat convection in surface tension and with the air-flow that rises in dry granulation device, be frozen into 1000 ~ The dilval granule of 1100 DEG C, falls in reforming reaction bed；
3) the dilval granule of reforming reaction bed is entered in the process continuing to fall and pile up in reforming reaction bed stop In, again carry out heat convection with the air-flow of rising in reforming reaction bed so that dilval particle temperature is down to 700 ~ 750 DEG C, then the discharging opening bottom reforming reaction bed is emitted into slag particle catcher and is collected, and the nickel in slag particle catcher Ferroalloy particles and water circulating and evaporating condenser carry out heat exchange so that the recirculated water in water circulating and evaporating condenser is by thermal evaporation Go out steam and by steam outlet, steam is delivered to the methane vapor air inlet of reforming reaction bed, hence into weight Reforming reaction is participated in whole reaction bed and dry granulation device；
4) in step 2) ~ 3) during, under the swabbing action of the air exhauster on gas channel, from methane vapor air inlet Enter reforming reaction bed methane vapor flow upwardly in dry granulation device, and in reforming reaction bed and dry granulation device with Dilval granule directly contacts, and is being heated and is occurring reforming reaction to generate an oxidation under the dilval effect as catalyst Carbon and hydrogen, the mixed gas that the methane vapor that then carbon monoxide, hydrogen are complete with unreacted is formed is from dry granulation device The gas outlet at top flows into gas channel, enters in entering the air-flow heat exchanger channels of water recycle heat exchanger after removing dust device dedusting Row heat exchange, the steam in mixed gas is condensed separation in the air-flow heat exchanger channels of water recycle heat exchanger, makes simultaneously The recirculated water of water recycle heat exchanger is heated and evaporates steam and be delivered to by steam by recirculated water heat exchange steam (vapor) outlet The methane vapor air inlet of reforming reaction bed, hence into participating in reforming reaction in reforming reaction bed and dry granulation device；Go Except the mixed gas of steam flows into methane separation device by the air-flow heat exchanger channels outlet of water recycle heat exchanger again so that Remove and discharge from methane gas outlet after the methane in the mixed gas of steam is separated in methane separation device, then pass through The methane vapor air inlet of reforming reaction bed participates in reforming reaction in coming back to reforming reaction bed and dry granulation device, and goes Except the carbon monoxide in the mixed gas of steam, hydrogen are arranged from mixed tail gas outlet with after methane separation in methane separation device Go out.
Compared to prior art, there is advantages that
1, the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device and method, have employed dry method grain Change method preferably ensures that the refinement to dilval is granulated effect, and additionally uses on this basis dilval waste heat money The Physical in source and the united three grades of recovery of chemical method so that the residual heat resources of dilval are used to as methane vapor weight The heat energy supply of whole reaction and chemical energy supply, and dilval delivers heat to gained mixed gas after reforming reaction by physics After heat energy and dilval heat transfer, the waste heat of self, then be used for converting generation steam and returning by two different phases Participate in reforming reaction, thus the supply that to reforming reaction bed in be passed through new steam is greatly decreased, reach minimizing methane water The purpose of the production cost of steam resource needed for steam reforming reaction, is effectively increased the recovery to dilval residual heat resources Efficiency and utilization rate.
2, in dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device and method, it is not necessary to Catalyst is additionally added for methane-steam reforming, and directly by dilval self as promoting methane vapor The catalyst of reforming reaction, is that the another kind to dilval resource utilizes form.
3, the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device and method are utilized, from nickel It is mixed that the methane separation device mixed tail gas outlet of ferroalloy dry granulation and methane vapor reforming waste-heat recovery device is discharged Close the mixed gas (i.e. water gas) that the main component in tail gas is carbon monoxide, hydrogen, the most not only do not contain industrial refuse Gas, it is to avoid extra industrial refuse processing cost, and water gas or a kind of more conventional industrial fuel and hydrogen manufacturing Raw material, is the industrial products very with industrial application value, further embodies the present invention program for more than dilval The Optimum utilization of thermal resource.
4, the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device and method, not only may be used For the reformation realizing methane vapor, it is also possible to for realizing the alkanes light hydrocarbon such as propane and steam Reform.
5, in the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device, additionally it is possible to by right In its dry granulation device, the structure of centrifugal granulation device is improved, and porous is centrifuged revolving cup to be granulated dilval, substantially increase from Heart granulating device utilizes efficiency to rotating energy, and then is favorably improved granulated processed efficiency.
6, dilval dry granulation and the methane vapor reforming waste-heat recovery device structure of the present invention are relatively simple, raw Produce and implement and use operation the most relatively simple, and combine its dilval dry granulation and methane vapor reforming waste heat recovery Method, while realizing the granulation processing of liquid molten dilval, additionally it is possible to the waste heat of state dilval is passed through physics The multistage recovery of method associating chemical method is converted into the resource requirement of methane-steam reforming, it is possible to helps to improve and closes ferronickel The recovery utilization rate of gold residual heat resources, thus effectively solve the granulation difficult processing melting dilval in prior art to meet not Rust steel smelting technological requirement and the low problem of its residual heat resources recovery utilization rate, have good industrial application value, Ke Yi Domestic smelter popularization and application.
Accompanying drawing explanation
Fig. 1 is that the one of dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device is preferable to carry out Structural representation.
Fig. 2 is centrifugal granulation device in dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device The porous of prioritization scheme is centrifuged revolving cup and is embodied as the sectional structure schematic diagram of structure.
Fig. 3 is the cooling slag particle figure of gained in the embodiment of the present invention three.
Detailed description of the invention
The granulation difficult processing being directed in prior art melted dilval requires and it to meet stainless steel-making process The problem that residual heat resources recovery utilization rate is low, needing starts with in terms of granulating technique, waste heat recovery two simultaneously solves.With The molten alloy granulating method of " pig machine ingot casting+Mechanical Crushing " is compared, and dry granulation method is made by centrifugal force by molten alloy Throw away so that cool and solidify as granule after the molten alloy droplets thrown away and convection gas heat exchange, it is achieved granulation, according to molten alloy Surface tension and viscous force, control the rotating speed of centrifugal granulation device in dry granulation device by appropriate, be then readily obtained 50mm The granulated product of following particle diameter, for the granulation of melted dilval is processed, such granulation granularity condition can be relatively The good requirement meeting stainless steel-making process.But, how to promote the waste heat during melted dilval dry granulation and return Rate of producing effects is again a new technical barrier, because if sharp after carrying out physics heat exchange only by convection gas and dilval The waste heat absorbed with gas carries out generation mode, still have that cogeneration efficiency is limited, residual heat resources recovery utilization rate relatively Low problem, so must take into the mode that residual heat resources are taked physical recovering method associating chemical recovering method, could improve remaining Thermal resource recovery utilization rate, meanwhile, the united waste heat chemical recovering method scheme of institute also needs to avoid dilval grain products Pollution, and, as the technology requirement in higher level face, the product of waste heat self gained of chemical recovering method scheme, the most not Industrial refuse to be contained, to avoid because increasing the overall one-tenth that the processing cost of gained industrial refuse causes waste heat recovery scheme This increase, even self products therefrom of waste heat chemical recovering method scheme are preferably able to as the industry product with industrial application value Product, the value that so dilval residual heat resources can be made to reclaim is maximized as far as possible.
Based on above-mentioned technical thought, in order to preferably solve in prior art the granulation difficult processing of melted dilval with Meet stainless steel-making process requirement and the low problem of its residual heat resources recovery utilization rate, the invention provides a kind of ferronickel and close Gold dry granulation and methane vapor reforming waste-heat recovery device, and utilize this device to carry out dilval dry granulation and first The method of alkane steam reforming waste heat recovery processing, while realizing the granulation processing of liquid molten dilval, additionally it is possible to Waste heat multistage recovery in addition to state dilval is converted into the resource requirement of methane-steam reforming, it is achieved that to waste heat The Physical of resource and the combined recovery of chemical method, thus help to improve the recovery utilization rate to dilval residual heat resources, and And waste heat chemical recovering method scheme products therefrom is water gas (main component is carbon monoxide and hydrogen), it is that there is commercial Application The industrial products that are worth and without industrial refuse product.
Below technical scheme is described in detail.
As it is shown in figure 1, the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device mainly by Dry granulation device 10, reforming reaction bed 20, slag particle catcher 30, water circulating and evaporating condenser 40, water recycle heat exchanger 50 and Methane separation device more than 60 part is constituted.Wherein, the top of dry granulation device 10 is provided with dilval liquid entrance 11 and gas outlet 12, the middle part in dry granulation device 10 is positioned at the position directly below of dilval liquid entrance and is provided with centrifugal granulation device 70, dry The bottom of method pelletizer 10 connects with the top of described reforming reaction bed 20 and is connected；The bottom of reforming reaction bed 20 is provided with funnel The discharging opening 21 of shape, and the sidewall that the bottom of reforming reaction bed 20 is near funnel-form discharging opening position is provided with methane vapor Air inlet 22, here, methane vapor air inlet can be provided only with one, it is also possible to is provided with multiple, and each methane Steam air inlet is used for being passed through methane vapor, methane gas or steam；Slag particle catcher 30 is the most just to being arranged at weight At unloading position below the discharging opening 21 of whole reaction bed, and water circulating and evaporating condenser 40 is arranged at the end of slag particle catcher 30 Portion and can and slag particle catcher between carry out conduction of heat, and the steam outlet 41 of water circulating and evaporating condenser 40 is communicated to weight The methane vapor air inlet 22 of whole reaction bed 20.The gas outlet 12 at dry granulation device 10 top is by being disposed with convulsion The gas channel of machine 13 and cleaner unit 14 is communicated to the air-flow heat exchanger channels entrance of water recycle heat exchanger 50, air exhauster 13 drive Moving air flow flows to the air-flow heat exchanger channels of water recycle heat exchanger 50 from dry granulation device 10；The air-flow of water recycle heat exchanger 50 Heat exchanger channels outlet is to the air inlet of methane separation device 60, and the recirculated water heat exchange steam (vapor) outlet of water recycle heat exchanger 50 The 51 methane vapor air inlets 22 being communicated to reforming reaction bed 20；Methane separation device 60 is then for separating from the gas entered Go out methane, and methane and the mixed tail gas of isolated are exported 62 rows from its methane gas outlet 61 and mixed tail gas respectively Go out, and the methane gas outlet 61 of methane separation device is also communicated to the methane vapor air inlet 22 of reforming reaction bed.
For being embodied as, at dilval dry granulation and the methane vapor reforming waste heat recovery dress of the present invention In putting, according to surface tension and the viscous force of melted dilval, filled by centrifugal granulation in appropriate control dry granulation device The rotating speed put, is easier to obtain the dilval granulated product of below 50mm particle diameter, it is possible to preferably meet stainless steel smelting work The requirement of skill.But in order to preferably ensure the granulation effect to dilval, the centrifugal granulation device in dry granulation device is permissible Using the structure design optimized, the rotation that the centrifugal granulation device of this optimized Structure Design is arranged straight up by drive shaft drives Motor and the porous being arranged in the drive shaft of rotary drive motor are centrifuged revolving cup and constitute；As in figure 2 it is shown, described porous is centrifuged Revolving cup 71 has 71a at the bottom of horizontally disposed glass and the wall of cup 71b extended straight up along cup feather edge, and porous is centrifuged revolving cup 71 opening up and be right against the dilval liquid entrance of dry granulation device, porous is centrifuged on the wall of cup 71b of revolving cup circumferentially Being provided with the through hole 71c being arranged into several rows from position at the bottom of cup from bottom to top, the thickness of described wall of cup is 5 ~ 10mm, described through hole Aperture be 10 ~ 20mm, the spacing being arranged between adjacent two through hole edges of same a line is 5 ~ 10mm, is arranged in adjacent two Spacing between adjacent two through hole edges of row is 6 ~ 15mm, and the through hole of every adjacent rows is staggered.This optimization structure Centrifugal granulation device have employed the porous of Unique physical design and be centrifuged revolving cup, porous is centrifuged the wall of cup of revolving cup and erects along cup feather edge Directly upwardly extend, and circumferentially arranged with being arranged into the through hole of several rows from bottom to top from position at the bottom of cup on wall of cup, thus from During heart granulation, enter porous and be centrifuged the top edge that the liquid molten dilval of revolving cup is difficult to from wall of cup and throw away, but It is forced in the through hole from wall of cup to squeeze under rotary centrifugal force effect and gushes, form the slag liquid that diameter is suitable with through-hole aperture Line, and subsequently break up, be granulated into molten drop, thus the generation of block slag and slag wool is greatly reduced；Porous is centrifuged on the wall of cup of revolving cup The aperture of through hole is 10 ~ 20mm, and the dilval molten drop size being thrown out of is limited by through-hole aperture, hence in so that ferronickel closes The cooling granulation particle diameter obtained after gold molten drop cooling is also mainly distributed on the interval of 10 ~ 20mm, it is not necessary to again carry out pulverization process Just can be directly used for stainless steel smelting to produce；Further, the through hole being centrifuged on revolving cup wall of cup due to porous from position at the bottom of cup from Lower and on be provided with multilamellar, during centrifugal granulation, in no matter porous is centrifuged revolving cup, the accumulation of melted dilval is less Or time more, can well make melted dilval through hole of differing heights from wall of cup gush out and be granulated, from And make porous be centrifuged revolving cup and can be good at adapting to the change of different liquid molten dilval feed rate, reduce equipment To melted dilval feed stream quantitative limitation, the most also make to rotate porous in granulation be centrifuged the rotation of revolving cup can It is fully utilized, centrifugal granulation device can be run with higher rotating speed, to improve granulated processed efficiency；Additionally, it is many It is 5 ~ 10mm that hole is centrifuged the thickness of revolving cup wall of cup, because wall of cup thickness is unsuitable excessive, and the otherwise axial length mistake of through hole on wall of cup Length is easily caused slag and adheres in through-holes, and then easily makes through hole block, and causes through hole utilization rate to decline；And centrifugal turn of porous Between through hole on cup wall of cup, the spacing being arranged between adjacent two through hole edges of same a line is 5 ~ 10mm, is arranged in phase Spacing between adjacent two through hole edges of adjacent two row is 6 ~ 15mm, and the through hole of every adjacent rows is staggered, and is so Ensure porous be centrifuged the distribution situation of through hole on revolving cup will not the most intensive and cause the slag liquidus gushed out from different through holes or Molten drop is mutually conglomeration again because of hypotelorism, impact granulation effect, also ensure through hole distribution situation will not the most sparse and Cause porous to be centrifuged the less slag causing the interior accumulation of revolving cup of number of openings on revolving cup wall of cup cannot quickly discharge.As can be seen here, There is the porous of this optimization design be centrifuged the centrifugal granulation apparatus structure of revolving cup and can preferably ensure the granulation to dilval Effect, and be centrifuged revolving cup by porous and be granulated dilval, it is possible to be greatly improved centrifugal granulation device to rotate can profit By efficiency, and then it is favorably improved granulated processed efficiency.
Additionally, in the dilval dry granulation of the present invention and being embodied as of methane vapor reforming waste-heat recovery device In, moving bed or fluid bed can be used in order to carry out the reforming reaction bed of methane-steam reforming, it is to avoid because of completely Redesign reforming reaction bed and increase device manufacturing cost.And methane separation device is mainly used for the one of reforming reaction generation Methane in the mixed gas that carbonoxide, the hydrogen methane vapor complete with unreacted is formed is separated with other gas, can To use stage variable pressure adsorption tower to be achieved, its concrete methane separation implementation belongs to prior art, is not the present invention Innovation point, at this no longer add narration.
The dilval dry granulation and the methane vapor reforming waste-heat recovery device that use the present invention implement dilval Dry granulation and the method for methane vapor reforming waste heat recovery, be embodied as step as follows:
1) startup optimization dilval dry granulation and methane vapor reforming waste-heat recovery device, controls in its dry granulation device Centrifugal granulation device rotary speed is 100 ~ 300rpm, and is passed through methane water in reforming reaction bed by its methane vapor air inlet Steam, in being driven dilval dry granulation and methane vapor reforming waste-heat recovery device by the air exhauster on gas channel Circulation of air flow；
2) the liquid molten dilval by 1600 ~ 1650 DEG C injects the dilval liquid entrance at dry granulation device top, flows into Centrifugal granulation device in dry granulation device, is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and in-flight Dilval molten drop carry out heat convection in surface tension and with the air-flow that rises in dry granulation device, be frozen into 1000 ~ The dilval granule of 1100 DEG C, falls in reforming reaction bed；
3) the dilval granule of reforming reaction bed is entered in the process continuing to fall and pile up in reforming reaction bed stop In, again carry out heat convection with the air-flow of rising in reforming reaction bed so that dilval particle temperature is down to 700 ~ 750 DEG C, then the discharging opening bottom reforming reaction bed is emitted into slag particle catcher and is collected, and the nickel in slag particle catcher Ferroalloy particles and water circulating and evaporating condenser carry out heat exchange so that the recirculated water in water circulating and evaporating condenser is by thermal evaporation Go out steam and by steam outlet, steam is delivered to the methane vapor air inlet of reforming reaction bed, hence into weight Reforming reaction is participated in whole reaction bed and dry granulation device；
4) in step 2) ~ 3) during, under the swabbing action of the air exhauster on gas channel, from methane vapor air inlet Enter reforming reaction bed methane vapor flow upwardly in dry granulation device, and in reforming reaction bed and dry granulation device with Dilval directly contacts, be heated and the dilval effect as catalyst under occur reforming reaction generate carbon monoxide and Hydrogen, the mixed gas that the methane vapor that then carbon monoxide, hydrogen are complete with unreacted is formed is from dry granulation device top Gas outlet flow into gas channel, after removing dust device dedusting enter water recycle heat exchanger air-flow heat exchanger channels in change Heat, the steam in mixed gas is condensed separation in the air-flow heat exchanger channels of water recycle heat exchanger, makes water follow simultaneously The recirculated water of ring heat exchanger is heated and evaporates steam and be delivered to reform by steam by recirculated water heat exchange steam (vapor) outlet The methane vapor air inlet of reaction bed, hence into participating in reforming reaction in reforming reaction bed and dry granulation device；Remove water The mixed gas of steam flows into methane separation device by the air-flow heat exchanger channels outlet of water recycle heat exchanger again so that remove Methane in the mixed gas of steam is discharged from methane gas outlet after being separated in methane separation device, then by reforming The methane vapor air inlet of reaction bed participates in reforming reaction in coming back to reforming reaction bed and dry granulation device, and removes water Carbon monoxide, hydrogen in the mixed gas of steam are discharged from mixed tail gas outlet with after methane separation in methane separation device.
The dilval dry granulation above-mentioned by the present invention and methane vapor reforming waste-heat recovery device and ferronickel thereof Alloy dry granulation and methane vapor reforming exhaust heat recovering method are it will be seen that present invention employs dry granulation method and come more preferably Ensure the refinement of dilval is granulated effect, and control centrifugal granulation device rotary speed in dry granulation device be 100 ~ 300rpm, reason is, according to surface tension and the viscous force analysis of liquid molten dilval, at the rotating speed of 100 ~ 300rpm Under the conditions of can preferably control dilval granulation particle diameter be mainly distributed on below 50mm, and, if combining above-mentioned optimization The centrifugal granulation device of structure, it is ensured that granularity dilval granular mass percentage ratio between 10 ~ 20mm accounts for 80 ~ 90% so that gained dilval grain graininess can better meet the requirement of stainless steel-making process.Meanwhile, to ferronickel Under conditions of alloy carries out dry granulation, the also residual heat resources to dilval have carried out Physical and united three grades of chemical method Reclaim.Wherein, first order waste heat recovery is to carry out in reforming reaction bed and dry granulation device, enters from methane vapor air inlet The methane vapor entered directly contacts with dilval in dry granulation device at reforming reaction bed, is conducted heat by physics and is subject to Heat, reaches the temperature conditions (more than 750 DEG C) needed for methane-steam reforming, and dilval becomes methane water and steams The catalyst of reforming reaction is there is so that methane and steam occur highly endothermic reforming reaction to generate carbon monoxide under upward adverse flow of QI temperature And hydrogen: CH4+ H2O → CO+3H2,ΔH=205.7kJ/mol；In the process, the waste heat of dilval is used to as first The chemical heat energy of alkane steam reforming reaction, after making to react also by physical thermal transmission, the mixed gas of gained is (main simultaneously Composition is the methane vapor that carbon monoxide, hydrogen and unreacted are complete) obtain substantial amounts of gas sensible heat, this process also makes The ferronickel that the liquid molten dilval of inject dry granulation device 1600 ~ 1650 DEG C is granulated into 1000 ~ 1100 DEG C by cooling closes Further by absorbing and cooling temperature to 700 ~ 750 DEG C after gold grain, then it is emitted into slag by the discharging opening bottom reforming reaction bed Grain catcher.And as second level waste heat recovery, under the swabbing action of the air exhauster on gas channel, at whole dilval In dry granulation and methane vapor reforming waste-heat recovery device, can be formed from reforming reaction bed to dry granulation device, again to water Recycle heat exchanger, arrive methane separation device again, be returned to the circulating current of reforming reaction bed, thus promote at reforming reaction bed and Have after reforming reaction in dry granulation device a large amount of sensible heat mixed gas (main component be carbon monoxide, hydrogen and The methane vapor that unreacted is complete) by entering the air-flow heat exchange of water recycle heat exchanger after the cleaner unit dedusting on gas channel In passage, carry out heat exchange with the recirculated water in the recirculated water heat exchanger channels of water recycle heat exchanger, during being somebody's turn to do, in mixed gas Steam be condensed in the air-flow heat exchanger channels of water recycle heat exchanger separation, make following of water recycle heat exchanger simultaneously Ring water is heated and evaporates steam and steam is delivered to by recirculated water heat exchange steam (vapor) outlet the methane water of reforming reaction bed Steam air inlet, as participating in the steam resource of reforming reaction in entering reforming reaction bed and dry granulation device, and due to The temperature of mixed gas sensible heat amount high, contained is big, therefore, it is possible to produce substantial amounts of steam by water recycle heat exchanger heat exchange It is supplied in reforming reaction.Third level waste heat recovery is to carry out, due to slag between slag particle catcher and water circulating and evaporating condenser Grain dilval particle temperature collected by catcher still reaches 700 ~ 750 DEG C, therefore is entered by water circulating and evaporating condenser The waste heat of dilval granule in one step recovery slag particle catcher, and water circulating and evaporating condenser is inhaled thermogenetic steam and is passed through Its steam outlet will be delivered to the methane vapor air inlet of reforming reaction bed, also serve as entering reforming reaction bed and dry method grain The steam resource of reforming reaction is participated in changing device.It can thus be seen that be combined by above-mentioned Physical and chemical method three Level waste heat recovery, the residual heat resources of dilval are used to the heat energy supply as methane-steam reforming and chemical energy supplies Should, and need not additionally add catalyst, dilval self then becomes the catalysis promoting methane-steam reforming Agent；And after dilval delivers heat to the heat energy of gained mixed gas after reforming reaction by physics and dilval conducts heat self Waste heat, then be used for converting by two different phases and produce steam return participation reforming reaction, thus be greatly decreased In reforming reaction bed, it is passed through the supply of new steam, reaches steam resource needed for minimizing methane-steam reforming The purpose of production cost, be effectively increased the organic efficiency to dilval residual heat resources and utilization rate.Moreover, pass through After above-mentioned process, from the methane separation device mixed tail gas of dilval dry granulation and methane vapor reforming waste-heat recovery device Main component in the mixed tail gas that outlet is discharged is the mixed gas (i.e. water gas) of carbon monoxide, hydrogen, the most not only Do not contain industrial refuse gas, it is to avoid extra industrial refuse processing cost, and water gas or a kind of more conventional Industrial fuel and hydrogen feedstock, be the industrial products very with industrial application value, further embody the present invention program Optimum utilization for dilval residual heat resources.Additionally, the dilval dry granulation of the present invention and methane vapor reforming Waste-heat recovery device and method, not only may be used for realizing the reformation of methane vapor, it is also possible to be used for realizing the alkane such as propane Hydro carbons light hydrocarbon and the reformation of steam, and there is similar know-why and effect.
Based on dilval dry granulation of the present invention and the know-why of methane vapor reforming waste-heat recovery device, as Further improvement project, as it is shown in figure 1, the water recycle heat exchanger 50 in device is additionally operable to collect in its air-flow heat exchanger channels Steam is cooled down the condensed water condensed and is discharged by condensed water delivery outlet 52, and the condensed water output of water recycle heat exchanger Mouth 52 is connected with the recirculated water water leg 42 of water circulating and evaporating condenser 40；Since so, the air-flow of water recycle heat exchanger Mixed gas in heat exchanger channels then can be collected by the condensed water that heat exchange is condensed and be delivered to water circulating and evaporating condenser Recirculated water water leg so that these condensed waters are used to be evaporated to slag particle catcher heat exchange in water circulating and evaporating condenser Steam, and then be again delivered back in reforming reaction bed and dry granulation device participating in reforming reaction, it is achieved to condensed water and Recycling of its cold resource.And as dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device Improvement project on the other hand, as it is shown in figure 1, in device between discharging opening 21 and the slag particle catcher 30 of reforming reaction bed 20 also Plate feed 80 can be had additional, process to the feeding and distributing material of slag particle catcher in order to carry out the discharging opening of reforming reaction bed； Since so, plate feed can be passed through so that fall into the slag particle of slag particle catcher at slag from the discharging opening of reforming reaction bed Grain catcher is laid more uniform, it is to avoid the slag particle in slag particle catcher is at the collection of reforming reaction bed discharging opening lower position In pile up and cause heat radiation inequality, thus be more beneficial for the slag particle in slag particle catcher and the heat between water circulating and evaporating condenser Conduction, it is possible to preferably ensure dilval granule in slag particle catcher with the heat exchange efficiency of water circulating and evaporating condenser.On Improvement project of both stating, is improved by the structure of not ipsilateral so that the dilval dry granulation of the present invention and methane Steam reforming waste-heat recovery device can possess more preferable heat recovery efficiency.
In addition it should be noted that methane-steam reforming involved in technical solution of the present invention, it has been The technology that one application is more ripe, the methane being therefore passed through needed for its reaction, the usage ratio of steam, be art technology Personnel can carry out grasping according to its technological know-how, further relates to dilval UTILIZATION OF VESIDUAL HEAT IN in technical solution of the present invention in addition In generation steam resource provisioning in reforming reaction, therefore in practical operation, those skilled in the art can close according to ferronickel The supply of gold waste heat output steam, suitable adjustment is additionally passed through methane, steam is supplied in the usage ratio of reforming reaction, Meet actual process operation demand.
In conjunction with embodiment, technical scheme and effect thereof are further described below.Should be appreciated that It is that these embodiments are only used for further illustrating embodiment of the present invention rather than for limiting the present invention.
Embodiment one:
Use dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device that melted dilval is carried out Granulation and waste heat recovery operate, and use the centrifugal granulation device of the optimization structure of present invention proposition in dry granulation device.Start Run dilval dry granulation and methane vapor reforming waste-heat recovery device, and by its methane vapor air inlet to weight It is passed through methane vapor in whole reaction bed, the air exhauster on gas channel drives dilval dry granulation and methane vapor Circulation of air flow in reformation waste-heat recovery device；Then the liquid dilval of about 1600 DEG C is injected dry granulation device top Dilval liquid entrance, flow into the centrifugal granulation device in dry granulation device, centrifugal granulation device used uses the present invention to carry The optimization structure gone out, its porous is centrifuged a diameter of 55 mm of revolving cup, and height is 135 mm, and wall of cup thickness is 5mm, logical on wall of cup The aperture in hole is 10mm, and the spacing being arranged between adjacent two through hole edges of same a line is 5mm, is arranged in adjacent rows Spacing between adjacent two through hole edges is 6mm, and controlling centrifugal granulation device rotary speed respectively is 100,200 and 300rpm, stream The liquid dilval entering centrifugal granulation device is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and in-flight Dilval molten drop surface tension and with dry granulation device in rise air-flow carry out heat convection, be frozen into 1000 DEG C The dilval granule of left and right, falls into and piles up funnelform discharging bottom reforming reaction bed after a period of time in reforming reaction bed Mouth is emitted into slag particle catcher and is collected, and the air-flow risen in dilval granule reforming reaction bed during being somebody's turn to do is carried out again Heat convection so that dilval particle temperature is down to about 700 DEG C, therefore the dilval granule in slag particle catcher is again Carry out heat exchange with water circulating and evaporating condenser, remained sensible heat and be converted into the steam needed for reforming reaction；And above-mentioned During, under the swabbing action of the air exhauster on gas channel, enter reforming reaction bed from methane vapor air inlet Methane vapor flows upwardly in dry granulation device, and direct with dilval granule in reforming reaction bed and dry granulation device Contact, is being heated and is occurring reforming reaction to generate carbon monoxide and hydrogen under the dilval effect as catalyst, and then one The mixed gas that carbonoxide, the hydrogen methane vapor complete with unreacted is formed gas outlet's stream from dry granulation device top Enter gas channel, in entering the air-flow heat exchanger channels of water recycle heat exchanger after removing dust device dedusting, carry out heat exchange, mixed gas In steam be condensed in the air-flow heat exchanger channels of water recycle heat exchanger separation, make water recycle heat exchanger simultaneously Recirculated water is heated and evaporates steam, thus the sensible heat of mixed gas is converted into the steam needed for reforming reaction, and removes The mixed gas of steam (is mainly composed of CH4, CO and H2) again by the air-flow heat exchanger channels outlet stream of water recycle heat exchanger Enter to methane separation device so that methane therein is discharged from methane gas outlet after being separated, and then generates with utilizing waste heat Steam is another with continuing cooling dilval granule in flowing back to reforming reaction bed and dry granulation device and participating in reforming reaction, and Remove the carbon monoxide in the mixed gas of steam, hydrogen to export from mixed tail gas with after methane separation in methane separation device Discharge, and then by mixed tail gas outlet, the mixed gas (water gas) of carbon monoxide, hydrogen can be collected and utilized, Such as in order to as fuel energy or hydrogen feedstock etc..The present embodiment is as shown in table 1 to the granulated processed result of dilval:
Table 1 embodiment one gained dilval grain graininess composition (wt%)
Embodiment two:
Use dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device that melted dilval is carried out Granulation and waste heat recovery operate, and use the centrifugal granulation device of the optimization structure of present invention proposition in dry granulation device.Start Run dilval dry granulation and methane vapor reforming waste-heat recovery device, and by its methane vapor air inlet to weight It is passed through methane vapor in whole reaction bed, the air exhauster on gas channel drives dilval dry granulation and methane vapor Circulation of air flow in reformation waste-heat recovery device；Then the liquid dilval of about 1630 DEG C is injected dry granulation device top Dilval liquid entrance, flow into the centrifugal granulation device in dry granulation device, centrifugal granulation device used uses the present invention to carry The optimization structure gone out, its porous is centrifuged a diameter of 55 mm of revolving cup, and height is 135 mm, and wall of cup thickness is 8mm, logical on wall of cup The aperture in hole is 15mm, and the spacing being arranged between adjacent two through hole edges of same a line is 8mm, is arranged in adjacent rows Spacing between adjacent two through hole edges is 10mm, and controlling centrifugal granulation device rotary speed respectively is 100,200 and 300rpm, stream The liquid dilval entering centrifugal granulation device is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and in-flight Dilval molten drop surface tension and with dry granulation device in rise air-flow carry out heat convection, be frozen into 1050 DEG C The dilval granule of left and right, falls into and piles up funnelform discharging bottom reforming reaction bed after a period of time in reforming reaction bed Mouth is emitted into slag particle catcher and is collected, and the air-flow risen in dilval granule reforming reaction bed during being somebody's turn to do is carried out again Heat convection so that dilval particle temperature is down to about 730 DEG C, therefore the dilval granule in slag particle catcher is again Carry out heat exchange with water circulating and evaporating condenser, remained sensible heat and be converted into the steam needed for reforming reaction；And above-mentioned During, under the swabbing action of the air exhauster on gas channel, enter reforming reaction bed from methane vapor air inlet Methane vapor flows upwardly in dry granulation device, and direct with dilval granule in reforming reaction bed and dry granulation device Contact, is being heated and is occurring reforming reaction to generate carbon monoxide and hydrogen under the dilval effect as catalyst, and then one The mixed gas that carbonoxide, the hydrogen methane vapor complete with unreacted is formed gas outlet's stream from dry granulation device top Enter gas channel, in entering the air-flow heat exchanger channels of water recycle heat exchanger after removing dust device dedusting, carry out heat exchange, mixed gas In steam be condensed in the air-flow heat exchanger channels of water recycle heat exchanger separation, make water recycle heat exchanger simultaneously Recirculated water is heated and evaporates steam, thus the sensible heat of mixed gas is converted into the steam needed for reforming reaction, and removes The mixed gas of steam (is mainly composed of CH4, CO and H2) again by the air-flow heat exchanger channels outlet stream of water recycle heat exchanger Enter to methane separation device so that methane therein is discharged from methane gas outlet after being separated, and then generates with utilizing waste heat Steam is another with continuing cooling dilval granule in flowing back to reforming reaction bed and dry granulation device and participating in reforming reaction, and Remove the carbon monoxide in the mixed gas of steam, hydrogen to export from mixed tail gas with after methane separation in methane separation device Discharge, and then by mixed tail gas outlet, the mixed gas (water gas) of carbon monoxide, hydrogen can be collected and utilized, Such as in order to as fuel energy or hydrogen feedstock etc..The present embodiment is as shown in table 2 to the granulated processed result of dilval:
Table 2 embodiment two gained dilval grain graininess composition (wt%)
Embodiment three:
Use dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device that melted dilval is carried out Granulation and waste heat recovery operate, and use the centrifugal granulation device of the optimization structure of present invention proposition in dry granulation device.Start Run dilval dry granulation and methane vapor reforming waste-heat recovery device, and by its methane vapor air inlet to weight It is passed through methane vapor in whole reaction bed, the air exhauster on gas channel drives dilval dry granulation and methane vapor Circulation of air flow in reformation waste-heat recovery device；Then the liquid dilval of about 1650 DEG C is injected dry granulation device top Dilval liquid entrance, flow into the centrifugal granulation device in dry granulation device, centrifugal granulation device used uses the present invention to carry The optimization structure gone out, its porous is centrifuged a diameter of 55 mm of revolving cup, and height is 135 mm, and wall of cup thickness is 10mm, logical on wall of cup The aperture in hole is 20mm, and the spacing being arranged between adjacent two through hole edges of same a line is 10mm, is arranged in adjacent rows Adjacent two through hole edges between spacing be 15mm, respectively control centrifugal granulation device rotary speed be 100,200 and 300rpm, The liquid dilval flowing into centrifugal granulation device is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and flight In dilval molten drop surface tension and with dry granulation device in rise air-flow carry out heat convection, be frozen into 1100 Dilval granule about DEG C, fall into reforming reaction bed is piled up after a period of time bottom reforming reaction bed funnelform go out Material mouth is emitted into slag particle catcher and is collected, and the air-flow risen in dilval granule reforming reaction bed during being somebody's turn to do enters again Row heat convection so that dilval particle temperature is down to about 750 DEG C, therefore the dilval granule in slag particle catcher Carry out heat exchange with water circulating and evaporating condenser again, remained sensible heat and be converted into the steam needed for reforming reaction；And upper During stating, under the swabbing action of the air exhauster on gas channel, enter reforming reaction bed from methane vapor air inlet Methane vapor flow upwardly in dry granulation device, and straight with dilval granule in reforming reaction bed and dry granulation device Contact, is being heated and is occurring reforming reaction to generate carbon monoxide and hydrogen, then under the dilval effect as catalyst The mixed gas that carbon monoxide, the hydrogen methane vapor complete with unreacted the is formed gas outlet from dry granulation device top Flow into gas channel, in entering the air-flow heat exchanger channels of water recycle heat exchanger after removing dust device dedusting, carry out heat exchange, gaseous mixture Steam in body is condensed separation in the air-flow heat exchanger channels of water recycle heat exchanger, makes water recycle heat exchanger simultaneously Recirculated water be heated and evaporate steam, thus the sensible heat of mixed gas is converted into the steam needed for reforming reaction, and goes Except the mixed gas of steam (is mainly composed of CH4, CO and H2) exported by the air-flow heat exchanger channels of water recycle heat exchanger again Flow into methane separation device so that methane therein is discharged from methane gas outlet after being separated, and then generates with utilizing waste heat Steam another with continuing cooling dilval granule in flowing back to reforming reaction bed and dry granulation device and participating in reforming reaction, And remove the carbon monoxide in the mixed gas of steam, hydrogen goes out from mixed tail gas with after methane separation in methane separation device Mouth is discharged, and then can be collected the mixed gas (water gas) of carbon monoxide, hydrogen and profit by mixed tail gas outlet With, such as in order to as fuel energy or hydrogen feedstock etc..The present embodiment granulated processed result such as table 3 institute to dilval Show:
Table 3 embodiment three gained dilval grain graininess composition (wt%)
Fig. 3 show in embodiment three the cooling slag particle obtained by granulation.By the cooling slag particle situation shown in Fig. 3, can see Arrive, use the cooling slag that dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device i.e. method obtain Grain, its vitrification degree is the highest, and its slag particle even particle size distribution, and sphericity is good, and slag wool is few, and granularity is mainly distributed In 10 ~ 20mm scope, it is possible to directly meeting stainless steel-making process requirement, the utilization rate of cooling slag particle is high.
In sum, the dilval dry granulation of the present invention and methane vapor reforming waste-heat recovery device structure are more Simply, produce and implement and use operation the most relatively simple, and combine its dilval dry granulation and methane vapor reforming Exhaust heat recovering method, while realizing the granulation processing of liquid molten dilval, additionally it is possible to the waste heat to state dilval The resource requirement of methane-steam reforming it is converted into, it is possible to help to improve by the multistage recovery of Physical associating chemical method Recovery utilization rate to dilval residual heat resources, thus effectively solve the granulation difficult processing of melted dilval in prior art To meet stainless steel-making process requirement and the low problem of its residual heat resources recovery utilization rate, there is good commercial Application valency Value, can smelter popularization and application at home.
Finally illustrating, above example is only in order to illustrate technical scheme and unrestricted, although with reference to relatively The present invention has been described in detail by good embodiment, it will be understood by those within the art that, can be to the skill of the present invention Art scheme is modified or equivalent, and without deviating from objective and the scope of technical solution of the present invention, it all should be contained at this In the middle of the right of invention.

Claims (7)

1. a dilval dry granulation and methane vapor reforming waste-heat recovery device, it is characterised in that include dry method grain Change device, reforming reaction bed, slag particle catcher, water circulating and evaporating condenser, water recycle heat exchanger and methane separation device；
The top of described dry granulation device is provided with dilval liquid entrance and gas outlet, and the middle part in dry granulation device is positioned at nickel Centrifugal granulation device, the bottom of dry granulation device and described reforming reaction bed it is provided with at the position directly below of ferroalloy liquid entrance Top connects connection；The bottom of reforming reaction bed is provided with funnelform discharging opening, and the bottom of reforming reaction bed is near funnel The sidewall of shape discharging opening position is provided with methane vapor air inlet；Described slag particle catcher is just to being arranged at reforming reaction bed Discharging opening below unloading position at, described water circulating and evaporating condenser be arranged at slag particle catcher bottom and can be with slag Carry out conduction of heat between grain catcher, and the steam outlet of water circulating and evaporating condenser is communicated to the methane water of reforming reaction bed Steam air inlet；
The gas outlet at described dry granulation device top is communicated to by being disposed with the gas channel of air exhauster and cleaner unit The air-flow heat exchanger channels entrance of water recycle heat exchanger, is driven air-flow to flow to the exchange of water cycling hot from dry granulation device by air exhauster The air-flow heat exchanger channels of device；The air-flow heat exchanger channels outlet of described water recycle heat exchanger is to the air inlet of methane separation device Mouthful, and the recirculated water heat exchange steam (vapor) outlet of water recycle heat exchanger is communicated to the methane vapor air inlet of reforming reaction bed；Institute State methane separation device for isolating methane from the gas entered, and by the methane of isolated and mixed tail gas respectively from it Methane gas outlet and mixed tail gas outlet are discharged, and the methane gas outlet of methane separation device is also communicated to reforming reaction bed Methane vapor air inlet.
Dilval dry granulation the most according to claim 1 and methane vapor reforming waste-heat recovery device, its feature It is, rotary drive motor that the centrifugal granulation device in described dry granulation device is arranged straight up by drive shaft and installation Porous in the drive shaft of rotary drive motor is centrifuged revolving cup and constitutes；Described porous is centrifuged revolving cup and has a horizontally disposed cup The end and the wall of cup extended straight up along cup feather edge, porous is centrifuged the opening up of revolving cup and is right against dry granulation device Dilval liquid entrance, porous is centrifuged on the wall of cup of revolving cup and is arranged into several rows from bottom to top circumferentially arranged with from position at the bottom of cup Through hole, the thickness of described wall of cup is 5 ~ 10mm, and the aperture of described through hole is 10 ~ 20mm, is arranged in adjacent two of same a line Spacing between through hole edge is 5 ~ 10mm, the spacing being arranged between adjacent two through hole edges of adjacent rows is 6 ~ 15mm, and the through hole of every adjacent rows is staggered.
Dilval dry granulation the most according to claim 1 and methane vapor reforming waste-heat recovery device, its feature Being, in described water recycle heat exchanger is additionally operable to collect its air-flow heat exchanger channels, steam cools down the condensed water condensed and leads to Cross condensation water output to discharge, and the recirculated water collection of the condensed water delivery outlet of water recycle heat exchanger and water circulating and evaporating condenser Tank is connected.
Dilval dry granulation the most according to claim 1 and methane vapor reforming waste-heat recovery device, its feature Being, described reforming reaction bed is moving bed or fluid bed.
Dilval dry granulation the most according to claim 1 and methane vapor reforming waste-heat recovery device, its feature Being, described methane separation device uses stage variable pressure adsorption tower.
Dilval dry granulation the most according to claim 1 and methane vapor reforming waste-heat recovery device, its feature It is, is provided with plate feed between discharging opening and the slag particle catcher of described reforming reaction bed, in order to carry out reforming reaction bed Discharging opening to the feeding of slag particle catcher.
7. a dilval dry granulation and methane vapor reforming exhaust heat recovering method, it is characterised in that use such as right Require that the dilval dry granulation described in 1 and methane vapor reforming waste-heat recovery device are implemented as follows:
1) startup optimization dilval dry granulation and methane vapor reforming waste-heat recovery device, controls in its dry granulation device Centrifugal granulation device rotary speed is 100 ~ 300rpm, and is passed through methane water in reforming reaction bed by its methane vapor air inlet Steam, in being driven dilval dry granulation and methane vapor reforming waste-heat recovery device by the air exhauster on gas channel Circulation of air flow；
2) the liquid molten dilval by 1600 ~ 1650 DEG C injects the dilval liquid entrance at dry granulation device top, flows into Centrifugal granulation device in dry granulation device, is thrown out of under centrifugal action, subsequently breaks up, is granulated into molten drop, and in-flight Dilval molten drop carry out heat convection in surface tension and with the air-flow that rises in dry granulation device, be frozen into 1000 ~ The dilval granule of 1100 DEG C, falls in reforming reaction bed；
3) the dilval granule of reforming reaction bed is entered in the process continuing to fall and pile up in reforming reaction bed stop In, again carry out heat convection with the air-flow of rising in reforming reaction bed so that dilval particle temperature is down to 700 ~ 750 DEG C, then the discharging opening bottom reforming reaction bed is emitted into slag particle catcher and is collected, and the nickel in slag particle catcher Ferroalloy particles and water circulating and evaporating condenser carry out heat exchange so that the recirculated water in water circulating and evaporating condenser is by thermal evaporation Go out steam and by steam outlet, steam is delivered to the methane vapor air inlet of reforming reaction bed, hence into weight Reforming reaction is participated in whole reaction bed and dry granulation device；
4) in step 2) ~ 3) during, under the swabbing action of the air exhauster on gas channel, from methane vapor air inlet Enter reforming reaction bed methane vapor flow upwardly in dry granulation device, and in reforming reaction bed and dry granulation device with Dilval granule directly contacts, and is being heated and is occurring reforming reaction to generate an oxidation under the dilval effect as catalyst Carbon and hydrogen, the mixed gas that the methane vapor that then carbon monoxide, hydrogen are complete with unreacted is formed is from dry granulation device The gas outlet at top flows into gas channel, enters in entering the air-flow heat exchanger channels of water recycle heat exchanger after removing dust device dedusting Row heat exchange, the steam in mixed gas is condensed separation in the air-flow heat exchanger channels of water recycle heat exchanger, makes simultaneously The recirculated water of water recycle heat exchanger is heated and evaporates steam and be delivered to by steam by recirculated water heat exchange steam (vapor) outlet The methane vapor air inlet of reforming reaction bed, hence into participating in reforming reaction in reforming reaction bed and dry granulation device；Go Except the mixed gas of steam flows into methane separation device by the air-flow heat exchanger channels outlet of water recycle heat exchanger again so that Remove and discharge from methane gas outlet after the methane in the mixed gas of steam is separated in methane separation device, then pass through The methane vapor air inlet of reforming reaction bed participates in reforming reaction in coming back to reforming reaction bed and dry granulation device, and goes Except the carbon monoxide in the mixed gas of steam, hydrogen are arranged from mixed tail gas outlet with after methane separation in methane separation device Go out.
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