CN107860238B - The commercial plant of zero-emission - Google Patents

The commercial plant of zero-emission Download PDF

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CN107860238B
CN107860238B CN201710955263.1A CN201710955263A CN107860238B CN 107860238 B CN107860238 B CN 107860238B CN 201710955263 A CN201710955263 A CN 201710955263A CN 107860238 B CN107860238 B CN 107860238B
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hydrogen
unit
gas
equipment
laipu
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CN107860238A (en
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贾鹏
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Shanghai Ke Laipu Energy Technology Co Ltd
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Shanghai Ke Laipu Energy Technology Co Ltd
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    • 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
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2

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  • Environmental & Geological Engineering (AREA)
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Abstract

The present invention a kind of method and commercial plant of zero-emission, including industrial furnace, combustion apparatus, Ke Laipu unit, transformation separation equipment, carbon dioxide purification equipment and peace hydrogen production unit, fuel and combustion-supporting gas generate the gas mixture based on carbon monoxide by the functional gasification of combustion apparatus progress；The exhanst gas outlet of industrial furnace connects harmful substance removal equipment by feed preheater or feed preheater and generator unit or flue gas heat-exchange unit or generator unit and flue gas heat-exchange unit；Harmful substance removal equipment is directly connected to or by Ke Laipu unit connection transformation separation equipment, the hydrogen outlet of transformation separation equipment is connected to peace hydrogen production unit, and the carbon dioxide outlet for converting separation equipment is connected to the fuel conveying gas entrance and combustion-supporting pipeline of carbon dioxide purification equipment, fuel conduit.The present invention is combined by functionality gasification with Ke Laipu unit, effectively removes the harmful substance in flue gas, the energy makes full use of, and is conducive to environment protection.

Description

The commercial plant of zero-emission
Technical field
The invention belongs to chemical industry, building materials and metallurgical production equipment technical field, it is related to a kind of commercial plant more particularly to one The commercial plant of kind zero-emission.
Background technique
The carbon dioxide content of atmosphere increases, and gradually enables global ocean souring.Scientist's estimation, to the end of this century, mistake The seawater of acid will lead to coral extinction, planktonic organism reduces, or even marine food chain is enabled to collapse.
Greenhouse effects are due to the phenomenon that carbon dioxide content increases, and Global Temperature increases in atmosphere.If carbon dioxide Content than now doubles, and Global Temperature will increase 3 DEG C~5 DEG C, and polar regions may increase 10 DEG C, and weather will obviously become It is warm.Temperature increases, and will lead to the increase of certain areas rainfall, certain areas drought, and hurricane strength enhances, and the frequency of occurrences also will It improves, natural calamity aggravation.More it is a concern that polar regions Melting Glacierss, sea level liter will be made since temperature increases Height, many coastal cities, island or low laying areas will face the threat of seawater rise, or even be swallowed up by seawater.60 years 20th century Dai Mo, the arid that African the Sahara pastoral area once continued 6 years.Due to lacking grain and herbage, livestock is slaughtered, hungry lethal Person is more than 1,430,000 people.Therefore, it is necessary to efficiently control carbon dioxide content increase, scientifical use fuel reinforces afforestation, Greening the earth prevents greenhouse effects from giving global bring huge disaster.
Carbon dioxide is to cause one of most important greenhouse gases of Global climate change, controls CO2 emission problem Extensive concern by countries in the world.Control greenhouse gas emission, mitigation of climate change have become China's the Implement of sustainable development The important component of strategy.
Energy-saving and emission-reduction are the manufacturing enterprise of the important topic that modern enterprise faces, especially industrial furnace, the recycling of waste heat It utilizes, not only protects environment, it is often more important that it is energy saving, reduce production cost.
Summary of the invention
The object of the present invention is to provide a kind of commercial plants of zero-emission to reduce energy to improve the thermal efficiency of heat energy apparatus Consumption, reduces and exhaust gas is avoided to discharge, environment protection is not contaminated.
A kind of commercial plant of zero-emission of the present invention, including industrial furnace, raw material cabin, product storehouse, fuel conduit and combustion-supporting Pipeline, the industrial furnace are equipped with combustion apparatus, feed inlet, discharge port, reactor product cooler and exhanst gas outlet, and the raw material cabin connects It is connected to feed inlet, the discharge port is connected to product storehouse by reactor product cooler, and described device is equipped with generator unit, raw material preheating Device, flue gas heat-exchange unit, harmful substance removal equipment, Ke Laipu unit, transformation separation equipment and carbon dioxide purification equipment, it is described Combustion apparatus is the burner, spray gun or burning beam being mounted in stove, or the functional gasification furnace being separately provided, the function Property gasification furnace be provided with the burner of fuel conduit and combustion-supporting pipeline, coal ash cooler and offgas outlet, fuel and combustion-supporting gas Body carries out functional gasification in the burner hearth or functional gasification furnace of industrial furnace, generates the gas mixing based on carbon monoxide Gas；The exhanst gas outlet of the industrial furnace connects harmful substance removal equipment by feed preheater, or passes through raw material preheating Device, generator unit connect harmful substance removal equipment, or connect harmful substance removal equipment, Huo Zhetong by flue gas heat-exchange unit Cross generator unit, flue gas heat-exchange unit connection harmful substance removal equipment；The harmful substance removal equipment is directly connected to or leads to Ke Laipu unit connection transformation separation equipment is crossed, transformation separation equipment is equipped with hydrogen outlet and carbon dioxide outlet, the hydrogen Outlet is connected to peace hydrogen production unit, and the carbon dioxide outlet is connected to the fuel of carbon dioxide purification equipment, combustion apparatus The fuel conveying gas entrance and combustion-supporting pipeline, the carbon dioxide purification equipment export of pipeline are connected to food-grade or technical grade two Carbonoxide finished pot；Ke Laipu unit passes through circulatory mediator pipeline and flue gas heat-exchange unit, product storehouse/product storehouse cooler, transformation Separation equipment, peace hydrogen production unit, coal ash cooler are separately connected to form circulation loop；The generator unit is cogeneration Equipment or/and differential pressure power generation equipment and Ke Laipu unit parallel power export or individually output.
The commercial plant of above-mentioned zero-emission, it is between the harmful substance removal equipment and transformation separation equipment or described The branch of setting connection carbon dioxide purification equipment between Ke Laipu unit and transformation separation equipment.
The commercial plant of above-mentioned zero-emission, the industrial furnace include partition rotary kiln, blast furnace, rotary kiln, beam type Shaft furnace, sleeve kiln or double-hearth lime kiln, the rotary kiln include lime rotary kiln, clinker rotary kiln, zero-emission calcium carbide time Rotary kiln, ironmaking rotary kiln or coking of coal rotary kiln；The generator unit is waste heat power generation equipment or differential pressure power generation equipment.
The commercial plant of above-mentioned zero-emission, the industrial furnace are partition rotary kiln or rotary kiln, and combustion apparatus is burner, Carbon dioxide gas seal box, the pressure of seal box are externally provided in the static and dynamic sealing part flap connecting with kiln head cover, kiln hood Higher than the kiln inner pressure of partition rotary kiln, the exhanst gas outlet of industrial furnace passes through feed preheater, waste heat power generation equipment, nuisance It is connect after matter removing equipment with Ke Laipu unit, Ke Laipu unit connection transformation separation equipment, the outlet for converting separation equipment connects Carbon dioxide purification equipment and peace hydrogen production unit are connect, Ke Laipu unit is cold by circulatory mediator pipeline and product storehouse/product storehouse But device, transformation separation equipment, peace hydrogen production unit are separately connected to form circulation loop；When helping in partition rotary kiln or rotary kiln When combustion gas body and fuel carry out gas mixture of the functional gasification reaction generation based on carbon monoxide, tail gas passes through Ke Laipu It is connect after unit with transformation separation equipment, tail gas is mixed by that can also be directly output as carbon monoxide after Ke Laipu unit at this time Close the industrial chemicals or gaseous fuel of gas；When tail gas as gaseous fuel in use, can use air as combustion-supporting gas into Promoting the circulation of qi, gaseous fuel are the gaseous mixture containing carbon monoxide, nitrogen and carbon dioxide；When in partition rotary kiln or rotary kiln When combustion-supporting gas and fuel carry out completely burned generation carbon dioxide, tail gas after Ke Laipu unit with carbon dioxide purification by setting Standby connection is not connect with transformation separation equipment, peace hydrogen production unit, and transformation separation equipment, peace hydrogen production unit are simultaneously stopped work Make；The burner of partition rotary kiln or rotary kiln can be arranged separately in inside kiln body, can also be substituted by functional gasification furnace, when When functional gasification furnace is arranged, Ke Laipu unit, which also passes through circulatory mediator pipeline and connect to be formed with coal ash cooler, to be recycled back to Road；Fuel carries out functional gasification by carbon dioxide wind model, by burner combustion, and functionality gasification is exactly fuel and gasification Agent pure oxygen/oxygen-enriched the imperfect combustion in partition rotary kiln generates carbon monoxide and a small amount of other gases, and when gasification adds part Carbon dioxide gas as diluent, and complete gasification while realize lime calcining, temperature control and deslagging multiple functions；When When combustion-supporting gas is the oxygen-enriched gaseous mixture with carbon dioxide, extra nitrogen and nitrogen oxides are removed by harmful substance removal equipment Impurity；Pure oxygen/oxygen-enriched and carbon dioxide mix gas ratio is 0: 100~100: 0 (volume ratio)；The partition rotary kiln kiln body is Tube-in-tube structure is made of coaxial mounted inner barrel and outer barrel, and the center of inner cylinder is kiln thorax, is led between inner barrel and outer barrel for material Road, the material channel, which is equipped with, supports resistance to material；Partition rotary kiln fuel passes heat in intermediate hearth combustion, by partition-wall heat transfer The raw material passed in annular space is calcined, since the continuous rotation of rotary kiln makes material thermally equivalent, and by feed end It slowly flows to discharge end, discharges after the completion of calcining.Combustion space is separated with calcination space, can produce high-purity not by flue gas The high-quality product of pollution isolation air heating.Functional gasification furnace is a kind of by pure oxygen/oxygen-enriched and carbon dioxide mix gas Imperfect combustion generates a large amount of heat formation with carbon monoxide high-temperature gas mixture as main component in gasification furnace with fuel Body supplies next industrial furnace and carries out heating or reduction reaction or the equipment that can also carry out protectiveness heating process, while in function The liquid lime-ash of fuel can be discharged out of the furnace in property gasification furnace.
The commercial plant of above-mentioned zero-emission, the partition rotary kiln are the segmented for being at least divided into one section according to temperature range Partition rotary kiln, be equipped with raw limestone storehouse, classification feeder, each section of partition rotary kiln be respectively equipped with feed inlet, discharge port, Wall calcines tonifying Qi entrance and decomposed gas outlet；The raw limestone storehouse is connected to classification feeder, classification feeder connection To classification feed inlet, each grading discharge mouth is connected to each classification lime silo；Each section of decomposed gas outlet is connected to two Carbonoxide equipment for purifying；The partition rotary kiln is exported equipped with fuel lime-ash；Rotary kiln burner both can only carry out completely burned It can also carry out functional gasification;Rotary kiln burner can also be replaced with individual device functionality gasification furnace, to generate high temperature Mixed gas based on carbon monoxide enters the kiln thorax of partition rotary kiln；In functionality gasification, the Ke Laipu unit is connected to Partition calcines tonifying Qi entrance, and calcined by rotary kiln tail gas is after Ke Laipu unit recovery waste heat, and extraction section low temperature exhaust gas is to calcining To enhance product performance, air compensation is that limestone calcination generates the 0~100% of tail gas amount for lime tonifying Qi.
The commercial plant of above-mentioned zero-emission, the rotary kiln are clinker rotary kiln, and the feed preheater setting is burnt Mouth, burner connect fuel conduit and combustion-supporting pipeline, and fuel and combustion-supporting gas carry out functional gasification in feed preheater, generate Gas mixture based on carbon monoxide；Or functional gasification furnace is set up outside feed preheater, functional gasification furnace Offgas outlet is connected to feed preheater.
The commercial plant of above-mentioned zero-emission, the industrial furnace are beam type shaft furnace, sleeve kiln or double-hearth lime kiln, the work Bottom gas cooled nozzle is arranged in the bottom of industry stove, and the exhanst gas outlet of industrial furnace is de- by flue gas heat-exchange unit, harmful substance Except equipment connects transformation separation equipment, the outlet connection carbon dioxide purification equipment and peace hydrogen production unit of separation equipment are converted, Setting is connected to the branch of carbon dioxide purification equipment, is connected to bottom between harmful substance removal equipment and transformation separation equipment The carbon monoxide of gas cooling spout supplements pipeline；Ke Laipu unit passes through circulatory mediator pipeline and flue gas heat-exchange unit, product storehouse Cooler, transformation separation equipment, peace hydrogen production unit are separately connected to form circulation loop；Combustion-supporting gas and combustion in industrial furnace When material carries out gas mixture of the functional gasification reaction generation based on carbon monoxide, tail gas passes through harmful substance removal equipment It is connect afterwards with transformation separation equipment, tail gas is by that can also be directly output as carbon monoxide after harmful substance removal equipment at this time The industrial chemicals or gaseous fuel of gaseous mixture；When the combustion-supporting gas and fuel progress completely burned generation titanium dioxide in industrial furnace When carbon, tail gas is connect after passing through harmful substance removal equipment with carbon dioxide purification equipment；The combustion apparatus of industrial furnace can be with It is arranged separately in inside kiln body, can also be substituted by functional gasification furnace, when functional gasification furnace is arranged, Ke Laipu unit is also It connect to form circulation loop with coal ash cooler by circulatory mediator pipeline；Fuel passes through burning by carbon dioxide wind model Mouth burning carries out functional gasification, and functionality gasification is exactly fuel and gasifying agent pure oxygen/oxygen-enriched incomplete in partition rotary kiln Burning generates carbon monoxide and a small amount of other gases, and when gasification adds partial CO 2 gas as diluent, and completes The multiple functions of lime calcining, temperature control and deslagging are realized while gasification；When combustion-supporting gas is the oxygen-enriched mixing with carbon dioxide When gas, extra nitrogen and N-oxide impurity are removed by harmful substance removal equipment；Pure oxygen/oxygen-enriched and carbon dioxide mix gas Ratio is 0: 100~100: 0 (volume ratio).
The commercial plant of above-mentioned zero-emission, the industrial furnace are beam type shaft furnace, and beam type shaft furnace is equipped with burning beam, burning beam It is interior that nozzles downward or to two sides are set, it is passed through cooling conduction oil in burning beam, conduction oil passes through thermally conductive oil circuit piping It connect to form circulation loop with Ke Laipu unit, the high temperature heat conductive oil of burning beam enters Ke Laipu unit and heat is transmitted to Ke Laipu Device reduces the temperature of conduction oil, and the conduction oil of low temperature is delivered in burning beam again.
The commercial plant of above-mentioned zero-emission, the industrial furnace are blast furnace, and the exhanst gas outlet of blast furnace passes through pressure Poor generating equipment, flue gas heat-exchange unit, harmful substance removal equipment are divided into two-way, and connection transformation separation equipment, another way are logical all the way It crosses the preset air inlet around the air inlet of blast furnace and is directly entered kiln thorax；The hydrogen outlet for converting separation equipment connects peace Hydrogen production unit, the carbon dioxide outlet for converting separation equipment are divided into three tunnels, are connected to carbon dioxide purification equipment all the way, all the way It is connected to fuel conduit, another way is connected to combustion-supporting pipeline；Ke Laipu unit passes through circulatory mediator pipeline and flue gas heat-exchange unit, production Product storehouse cooler, transformation separation equipment, peace hydrogen production unit are separately connected to form circulation loop.
The commercial plant of above-mentioned zero-emission, the Ke Laipu unit include expanding machine, generator, hydrogen heat compression device and Resuperheater；The expander outlet is connected to expander inlet, the expanding machine and power generation by hydrogen heat compression device Arbor connection, the generator are connect with external power circuit system.
The commercial plant of above-mentioned zero-emission, the hydrogen heat compression device are equipped with 2~100 groups of metal hydride reaction beds, The metal hydride reaction bed absorbs low pressure hydrogen at low temperature, releases high pressure hydrogen at high temperature；2~100 groups of gold Belong to hydride reaction bed and is arranged to one or more levels, when being set as level-one, the suction hydrogen temperature of metal hydride reaction bed in peer Identical, hydrogen discharging temperature is also identical；When being set as multistage, every grade of at least 2 groups of metal hydride reaction beds, upper level metal hydride The hydrogen discharging temperature of object reaction bed is higher than the hydrogen discharging temperature of next stage metal hydride, and the suction hydrogen temperature of upper level is also above next stage Suction hydrogen temperature, upper level metal hydride reaction bed inhale hydrogen when release heat supply next stage metal hydride reaction bed make With realizing the cascade utilization of heat；The expanding machine is multiple expansion engine, and every level-one is equipped with bleeding point and air inlet, upper level Outlet port the air inlet of next stage is connected to by resuperheater.Ke Laipu unit adds hydrogen storage material tank and gating system, leads to Cross strength, fluid power or mechanical system are realized between grade or metal hydrogen storage material between any two metal hydride reaction bed in grade Mutually switch.The Ke Laipu unit can add Organic Rankine Cycle low-temperature cogeneration device, further increase efficiency；It is organic Rankine cycle low-temperature cogeneration device includes evaporator, expanding machine, condenser, working medium pump and generator, is had using low boiling point Machine object is as working medium；Evaporator outlet is connected to expander inlet, and expander outlet is connected to condenser inlet, condensator outlet It is connected to evaporator inlet by working medium pump, expanding machine is connect with generator shaft；ORC (organic Rankine cycle) low-temperature device for generating power by waste heat Expanding machine and generator or be independently arranged, or shared with the original expanding machine of Ke Laipu unit and generator；Needed for evaporator The low temperature exhaust heat of heat and flue gas released when inhaling hydrogen from metal hydride reaction bed of heat.
The commercial plant of above-mentioned zero-emission, the peace hydrogen production unit, including at least two hydrogen abstraction reaction devices, metal hydrides Object more changing device, weary metal hydride container and saturation metal hydride container；The weary metal hydride container dress Have and discharge the metal hydrogen storage material after hydrogen by metal hydride, the saturation metal hydride container is equipped with by metal hydrogen storage Material absorbs the metal hydride formed after hydrogen, and the metal hydride outlet of the hydrogen abstraction reaction device passes through metal hydride more Changing device is connect with weary metal hydride container and saturation metal hydride container respectively, and the metal hydride more changes the outfit Set by strength, fluid power or mechanical system complete metal hydrogen storage material in weary metal hydride container enter hydrogen abstraction reaction device, And the metal hydrogen storage material in hydrogen abstraction reaction device absorbs the metal hydride formed after hydrogen and enters saturation metal hydride collection The material transfer process of vanning；The hydrogen abstraction reaction device connect to form circulation by cycle heat exchange medium pipeline with Ke Laipu unit Circuit, metal hydrogen storage material hydrogen abstraction reaction process releases a large amount of heat in hydrogen abstraction reaction device, by cycle heat exchange medium pipeline Cycle heat exchange medium indirect heat exchange take out of, heat exchange give Ke Laipu unit power generation, which may be hydrogen, directly The heat that the releasing of hydrogen abstraction reaction process is taken in heat exchange out of is connect, heat exchange generates electricity to Ke Laipu unit.The magnesium produced by peace hydrogen production unit Be metal hydride when in use, the releasing of hydrogen uses following either type: first is that magnesium system metal hydride is heated to Hydrogen is released after set temperature；Second is that water or water vapour, which is added, as auxiliary agent while heating releases hydrogen；Third is that in magnesium system After hydrogen release of the heated progress of metal hydride is decomposed into magnesium simple substance, then fills into water or water vapour and react generation hydrogen with magnesium simple substance Carry out secondary hydrogen release.
The commercial plant of above-mentioned zero-emission, the fuel are the single-fuel or any of carbon containing liquid, solid or gas Two or more fuel combinations；Fuel and combustion-supporting gas completely burned or functional no nitrogen that gasifies in entire production process It participates in, only micro nitrogen oxides generates；The whole hermetically sealed isolation air of entire process units, prevents air from entering system band Enter nitrogen；Pure oxygen source: the water electrolysis hydrogen productions by-product oxygen such as 1. clean energy resource, including wind-powered electricity generation, solar power generation；2. Ke Laipu is mono- Member power generation oxygen processed.
The commercial plant of above-mentioned zero-emission, the purposes of carbon dioxide: 1. normal usage；2. underground, ocean landfill, and needing It extracts out and recycles when wanting；3. stereo farm, three-dimensional pasture, three-dimensional tea plantation use；The present invention is suitable for having calcining heating, reproducibility The occasion of atmosphere, the heating of reduction protection atmosphere, including non-ferrous metal, ferrous metal, cement, lime, using carbonate as raw material Production, isolation air calcination product, cogeneration, low-temperature heat quantity recycling, the peace production of hydrogen production, carbon dioxide return It receives.
The present invention carries out a variety of traditional handicraft devices such as existing lime production, blast furnace, manufacture of cement, calcium carbide production Improve, make it on the basis of keeping original production function constant, moreover it is possible to change production model and carry out functional gasification, thus real A variety of traditional products such as lime, the pig iron, cement, calcium carbide are showed and have pacified the Poly-generation of hydrogen production, carbon dioxide and electric power, has had and produce Quality height, good in economic efficiency advantage；And by further setting Ke Laipu unit, the waste heat of process units is made full use of, The thermal efficiency is improved, energy-saving effect is good.The present invention not only effectively removes the harmful substance in flue gas simultaneously, has also recycled whole two Carbonoxide is conducive to environment protection, clean and environmental protection.
Detailed description of the invention
Fig. 1 is the flow diagram of the commercial plant of zero-emission of the present invention；
Fig. 2 is the flow diagram of another embodiment of the present invention；
Fig. 3 is the flow diagram of the third embodiment of the invention；
Fig. 4 is the flow diagram of the 4th kind of embodiment of the invention；
Fig. 5 is the flow diagram of the 5th kind of embodiment of the invention；
Fig. 6 is the flow diagram of the 6th kind of embodiment formula of the invention；
Fig. 7 is the flow diagram of the 7th kind of embodiment of the invention；
Fig. 8 is the flow diagram of the 8th kind of embodiment of the invention；
Fig. 9 is the flow diagram of the 9th kind of embodiment of the invention；
Figure 10 is the schematic diagram of Ke Laipu unit；
Figure 11 is the schematic diagram for pacifying hydrogen production unit；
Figure 12 is the structural schematic diagram of partition rotary kiln；
Figure 13 is the flow diagram of the tenth kind of embodiment of the invention；
Figure 14 is a kind of schematic diagram that Ke Laipu unit adds Organic Rankine Cycle low-temperature cogeneration device；
Figure 15 is another schematic diagram that Ke Laipu unit adds Organic Rankine Cycle low-temperature cogeneration device；
Figure 16 is the tenth a kind of flow diagram of embodiment of the invention.
Wherein: 1-partition rotary kiln, 2-waste heat power generation equipments, 3-Ke Laipu units, 4-transformation separation equipments, 5- Carbon dioxide purification equipment, 6-peace hydrogen production units, 7-beam type shaft furnaces, 8-burning beams, 9-flue gas heat-exchange units, 10-bis- thoraxes Limekiln, 11-bulk lime silos, 12-middle lump lime storehouses, 13-fritter lime silos, 14-powder lime silos, 15-bulks into Material mouth, 16-middle block feed inlets, 17-fritter feed inlets, 18-powder feed inlets, 19-classification feeders, 20-lime stones are former Feed bin, 21-decomposed gas outlets, 22-expanding machines, 23-generators, 24-partitions calcine tonifying Qi entrance, 25-cycle heat exchanges Medium pipeline, 26-hydrogen heat compression devices, 27-resuperheaters, 28-fuel inlets, 29-bottom gas cooled nozzles, 30-functional gasification burner tips, 31-feed inlets, 32-blast furnaces, 33-rotary kilns, 34-feed preheaters, 35-functions Property gasification furnace, 36-reactor product coolers, 37-harmful substance removal equipment, the outlet of 38-fuel lime-ash, 39-differential pressure power generations set Standby, 40-two hydrogen abstraction reaction devices, 41-metal hydrides more changing device, 42-weary metal hydride containers, 43-saturations It is metal hydride container, 44-sleeve kilns, 45-thermally conductive oil circuit pipings, 46-burners, 47-ash-dregs coolers, 48-close Joint sealing, 49-carbon dioxide finished pots, 50-inner cylinders, 51-kiln thoraxes, the 52-resistance to materials of support, 53-material channels, 54-outer cylinders, 55-shaft furnaces, 56-condensers, 57-working medium pumps, 58-evaporators.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in detail.The scope of protection of the present invention is not limited to the embodiment, Those skilled in the art make any change within the scope of the claims and also belong to the scope of protection of the invention.
Embodiment 1
Zero-emission commercial plant of the present invention is as shown in Figure 1, production active lime, carbon dioxide, peace hydrogen production and electric power are defeated By-product coal ash and sulfur-bearing product simultaneously out, including partition rotary kiln 1, raw limestone storehouse 20, lime silo, coke powder pipeline and pure Oxygen pipeline, partition rotary kiln are equipped with feed inlet, discharge port, exhanst gas outlet and fuel lime-ash outlet 38, and combustion apparatus is burner 46. Partition rotary kiln 1 is four-part form partition rotary kiln, and each section is respectively equipped with feed inlet, discharge port, partition rotary kiln tonifying Qi entrance 24 With decomposed gas outlet 21.Feed inlet includes bulk feed inlet 15, middle piece of feed inlet 16, fritter feed inlet 17 and powder feed inlet 18, discharge port includes bulk discharge port, middle piece of discharge port, fritter discharge port and discharge of fine material mouth.Raw limestone storehouse 20 passes through It is connected to feed inlet after classification feeder 19, the carbon dioxide tail gas heat exchange generated with lime burning, discharge port is connected to lime Storehouse.It is externally provided with carbon dioxide gas seal box 48 in the static and dynamic sealing part flap connecting with kiln head cover, kiln hood, seal box Pressure is higher than the kiln inner pressure of partition rotary kiln, guarantees that the gas in partition rotary kiln effectively completely cuts off with outside air.Partition returns Ke Laipu unit 3, transformation separation equipment 4, carbon dioxide purification equipment 5, harmful substance removal equipment 37 and peace are equipped with after rotary kiln Hydrogen production unit 6.The burner 46 of fuel conduit and pure oxygen piping connection to partition rotary kiln.Exhanst gas outlet is set by cogeneration Standby 2, harmful substance removal equipment 37 and Ke Laipu unit are connect with transformation separation equipment 4.Ke Laipu unit 3 is divided into two after coming out Road, is connected to carbon dioxide purification equipment 5 all the way, is connected to transformation separation equipment 4 all the way.Transformation separation equipment goes out equipped with hydrogen Mouth and carbon dioxide outlet, hydrogen outlet are connected to peace hydrogen production unit 6, and carbon dioxide outlet is connected to carbon dioxide purification and sets For 5 and the fuel conveying gas entrance and combustion-supporting gas pipeline of burner.The fuel conveying gas of coke powder piping connection to combustion apparatus enters Mouthful, carbon dioxide purification equipment export is connected to food-grade or industrial grade carbon-dioxide finished pot 49.Ke Laipu unit is by following Ring heat transferring medium pipeline 25, with peace hydrogen production unit 6, bulk lime silo 11, middle lump lime storehouse 12, fritter lime silo 13, powder Lime silo 14, and transformation separation equipment 4 are separately connected to form circulation loop, recycle the waste heat of these equipment: peace hydrogen production unit 6 Interior magnesium system metal inhale hydrogen release heat, the sensible heat of four lime silo high temperature products, convert separation equipment 4 in carbon monoxide with Vapor reaction generates the chemical reaction heat that carbon dioxide and hydrogen are released.The cycle heat exchange medium pipeline of Ke Laipu unit connection For 25 cycle heat exchange medium using the low temperature exhaust gas after heat exchange, main component is carbon monoxide or carbon dioxide.Low-temperature circulating changes Thermal medium comes out from Ke Laipu unit, by pacifying hydrogen production unit 6, bulk lime silo 11, middle lump lime storehouse 12, fritter lime silo 13, powder lime silo 14, and transformation separation equipment 4 return to Ke Laipu unit after the waste heat heat exchange heating for recycling these equipment.
A kind of condition of production of partition rotary kiln 1 are as follows: the combustion-supporting gas of burner 46 is gaseous mixture, mixed proportion oxygen: two Carbonoxide 99: 1, coke powder carry out functional gasification by carbon dioxide wind model to burner, and functionality gasification is exactly raw material coke powder Imperfect combustion generates carbon monoxide in partition rotary kiln with gasifying agent pure oxygen and other gases, when gasification can add portion on a small quantity Divide carbon dioxide gas as diluent；And the multiple functions of lime calcining, temperature control and deslagging are realized while completing gasification. Gasification temperature is 1430 DEG C, and the temperature of calcined kiln exit gas is up to 1000 DEG C, exhanst gas outlet by waste heat power generation equipment 2, It is connect after harmful substance removal equipment 37 with Ke Laipu unit 3, transformation separation equipment 4 is connected to after coming out from Ke Laipu unit 3. Ke Laipu unit is connected to partition calcining tonifying Qi entrance 24, and calcined by rotary kiln tail gas extracts after Ke Laipu unit recovery waste heat Part low temperature exhaust gas gives lime burning tonifying Qi, and air compensation is that limestone calcination generates 1% or so of tail gas amount, low supplemented with part It after warm tail gas, carries out the calcining of lime stone under carbon monoxide, hydrogen atmosphere, improve Activity of Lime, calcinating speed and forges Burn quality.
Another condition of production of partition rotary kiln 1 are as follows: coke powder and pure oxygen gaseous mixture (mixed proportion oxygen: carbon dioxide 30: 70) completely burned generates carbon dioxide in burner, generates 1500 DEG C of high temperature, the temperature of calcined kiln exit gas is up to 1050 DEG C, exhanst gas outlet is come by connecting after waste heat power generation equipment 2, harmful substance removal equipment 37 with Ke Laipu unit 3 from Ke Pu unit 3 is directly connected to carbon dioxide purification equipment 5 after coming out, without using transformation separation equipment 4, peace hydrogen production unit 6.It mentions Carbon dioxide after pure enters finished pot all the way, and another way is connected to the fuel conveying gas entrance and combustion-supporting gas pipeline of burner.
The operational process of zero-emission commercial plant of the present invention are as follows: the lime stone in raw limestone storehouse 20 is sent through conveying equipment To classification feeder 19, according to grade classification respectively through bulk feed inlet 15, middle piece of feed inlet 16, fritter feed inlet 17 and powder After feed inlet 18, with the heat exchange of calcining and decomposing gas high temperature carbon dioxide, into the annular materials space of each section of partition rotary kiln.Bulk The partial size of lime stone is 1~5mm, and middle lump lime stone grain diameter is 50 mesh~1mm, and the partial size of fritter lime stone is 50~100 mesh, powder The partial size of material is 100 mesh or less.Purity oxygen and carbon dioxide mix ratio oxygen: carbon dioxide 99: 1, it is combustion-supporting into burner, by Carbon dioxide is conveying power wind, and conveying coke powder fuel enters burner combustion and carries out functional gasification, calcining and gasification simultaneously into Row generates 1430 DEG C of high temperature, calcines the limestone material in each section of annular materials space of partition rotary kiln, lime is through each discharge port Into the product storehouse of each grade.What is generated in calcination process decomposes gas through each section of decomposed gas outlet 21, into titanium dioxide Carbon equipment for purifying 5 purifies.The outlet temperature of calcined burner hearth flue gas is up to 1000 DEG C, through exhanst gas outlet to waste heat power generation equipment Power generation, the flue gas after power generation are sent out to Ke Laipu unit using low-temperature heat source after harmful substance removal equipment deviates from harmful substance Electricity, it is defeated outside electricity to be connected to the grid.The gas for leaving Ke Laipu unit isolates hydrogen and titanium dioxide to transformation separation equipment 4 Carbon, for the hydrogen separated through peace hydrogen production unit production peace hydrogen production, the carbon dioxide a part separated enters carbon dioxide purification Equipment 5 goes out device as industrial grade carbon-dioxide after purification, and a part to pure oxygen pipeline adjusts combustion-supporting gas oxygen content, with control Calcination temperature processed, some provides power wind to fuel pump deliver line for coke powder conveying.The circulation of Ke Laipu unit connection The cycle heat exchange medium of heat transferring medium pipeline 25 is the low temperature exhaust gas after heat exchange, and calcined by rotary kiln tail gas is recycled through Ke Laipu unit After waste heat, part low temperature exhaust gas gives cycle heat exchange medium, and main component is carbon monoxide or carbon dioxide.Low-temperature circulating heat exchange is situated between Matter comes out from Ke Laipu unit, individually by peace hydrogen production unit 6, bulk lime silo 11, middle lump lime storehouse 12, fritter stone It is mono- to return to Ke Laipu after the waste heat heat exchange heating for recycling these equipment for ash cellar 13, powder lime silo 14, and transformation separation equipment 4 Member generates electricity heat to Ke Laipu unit.1 fuel of partition rotary kiln is transferred heat in intermediate hearth combustion by partition Raw limestone in annular space is calcined, since the continuous rotation of rotary kiln makes material thermally equivalent, and by feeding End is slowly flowed to discharge end, is discharged after the completion of calcining.Combustion space is separated with calcination space, can produce high-purity not by cigarette The high-quality lime of gas pollution.The partition space of partition rotary kiln is divided into four sections, it is therefore an objective to calcine the lime of different-grain diameter respectively Stone raw material, in high temperature section calcining, middle fritter in medium temperature section calcining, powder in low temperature section calcining, effective use passes bulk lime stone The hot temperature difference and heat grade.Waste heat power generation equipment 2 includes mainly steam boiler, steam turbine and generator, and operational process is steam The waste heat that boiler recycles 1000 DEG C of burner hearth flue gases of partition rotary kiln generates precritical high temperature and high pressure steam, and pushing turbine drives Electrical power generators are respectively or in parallel outer defeated with 3 electricity of Ke Laipu unit.
As shown in Figure 10, Ke Laipu unit includes expanding machine 22, generator 23, hydrogen heat compression device 26 and resuperheat Device 27.Expander outlet is connected to expander inlet by hydrogen heat compression device, and expanding machine is connect with generator shaft, generator It is connect with external power circuit system.Ke Laipu unit is using the principle of cogeneration: by cycle heat exchange medium pipeline 25 Cycle heat exchange medium, the waste heat in device is recycled and is exchanged heat to hydrogen heat compression device 26 and resuperheater 27.Hydrogen As acting medium, is reacted in hydrogen heat compression device 26 under low-temp low-pressure with rare earth metal and generate metal hydride, it should The hydrogen that high temperature and pressure is released after metal hydride is heated pushes expanding machine acting power generation, in expansion process extraction it is intermediate again Heating improves the acting ability of hydrogen in hot device 27, returns to hydrogen hot pressing from the low-temp low-pressure hydrogen after the acting that expanding machine comes out Contracting equipment 26 inhales hydrogen recycling again.Hydrogen heat compression device 26 has six hydrogen heat compression reactors, every alternately inhale hydrogen, Hydrogen release.
In actual production, Ke Laipu unit can also be transformed to diversified forms, such as cascade utilization form or add organic bright The form for agreeing circulation low-temperature cogeneration device guarantees the waste heat source using various temperature.So-called cascade utilization form is Refer to that the hydrogen heat compression device 26 is equipped with 2~100 groups of metal hydride reaction beds, the metal hydride reaction bed is in low temperature Lower absorption low pressure hydrogen, releases high pressure hydrogen at high temperature；2~100 groups of metal hydride reaction beds are arranged to multistage, often The hydrogen discharging temperature of grade at least 2 groups of metal hydride reaction beds, upper level metal hydride reaction bed is higher than next stage metallic hydrogen The hydrogen discharging temperature of compound, suction suction hydrogen temperature of the hydrogen temperature also above next stage of upper level, upper level metal hydride reaction bed The heat supply next stage metal hydride reaction bed released when inhaling hydrogen uses, and realizes the cascade utilization of heat；The expanding machine 22 be multiple expansion engine, and every level-one is equipped with bleeding point and air inlet, and the outlet port of upper level is connected to by resuperheater 27 The air inlet of next stage.
Ke Laipu unit adds Organic Rankine Cycle low-temperature cogeneration device, further increases efficiency；Organic Rankine follows Ring low-temperature cogeneration device includes evaporator 58, expanding machine 22, condenser 56, working medium pump 57 and generator 23, using low boiling Point organic matter is as working medium；The heat and flue gas that heat needed for evaporator 58 is released when inhaling hydrogen from metal hydride reaction bed Low temperature exhaust heat；The outlet of evaporator 58 is connected to 22 entrance of expanding machine, and the outlet of expanding machine 22 is connected to 56 entrance of condenser, condenses The outlet of device 56 is connected to 58 entrance of evaporator, expanding machine 22 and 23 axis connection of generator by working medium pump 57.Organic Rankine Cycle The expanding machine and generator of potential temperature device for generating power by waste heat are independently arranged as shown in figure 14, or as shown in figure 15 with Ke Laipu unit Original expanding machine and generator share.When sharing, expanding machine 22 adds level-one organic working medium compressor and level-one organic working medium Expanding machine, after the organic working medium steam come out from evaporator is introduced into the compression of organic working medium compressor, then to be sent to organic working medium swollen Swollen machine expansion work, the organic working medium steam after acting send back to condenser recycling.
As shown in figure 11, pacify hydrogen production unit 6, including two hydrogen abstraction reaction devices 40, metal hydrides more changing device 41, weary Metal hydride container 42 and saturation metal hydride container 43.Hydrogen abstraction reaction device is equipped with as main component with magnesium metal Metal hydrogen storage material.Hydrogen abstraction reaction device connect to form circulation loop with Ke Laipu unit 3 by cycle heat exchange medium pipeline 25, and two Platform hydrogen abstraction reaction device metal hydride outlet by metal hydride more changing device respectively with weary metal hydride container 42 It is connected with saturation metal hydride container 43.Peace 6 working principle of hydrogen production unit is: hydrogen source is in the change of each process units Separation equipment 4 is changed, the weary metal hydride in weary metal hydride container uses circulation and stress after hydrogen from user Metal is added to hydrogen and weary metal hydride in hydrogen abstraction reaction device 40, and weary metal hydride is allowed to absorb hydrogen reaction production It is saturated metal hydride, the saturation metal hydride of production is added in saturation metal hydride container 43, uses protective gas User's use is transported in sealing, and hydrogen abstraction reaction process releases a large amount of heat, by the cycle heat exchange in cycle heat exchange medium pipeline 25 Medium indirect heat exchange is taken out of, and heat exchange generates electricity to Ke Laipu unit 3.The cycle heat exchange medium may be hydrogen, directly heat exchange band The heat that hydrogen abstraction reaction process is released out, heat exchange generate electricity to Ke Laipu unit 3.The effect of metal hydride more changing device 41 is, By air-flow conveying by weary metal hydride from Alternating Transportation after the extraction of weary metal hydride container 42 to two hydrogen abstraction reactions In device 40, and saturation metal hydride is conveyed by air-flow and extracts Alternating Transportation out from two hydrogen abstraction reaction devices 40 to saturation gold Belong to hydride container 43.
When the magnesium system metal hydride produced by peace hydrogen production unit 6, the releasing of its hydrogen uses following when in use One mode: first is that releasing hydrogen after magnesium system metal hydride is heated to set temperature；Second is that heating while be added water or Water vapour releases hydrogen as auxiliary agent；Third is that after hydrogen release of the heated progress of magnesium system metal hydride is decomposed into magnesium simple substance, then It fills into water or water vapour and reacts the secondary hydrogen release of generation hydrogen progress with magnesium simple substance.
Embodiment 2
Second of embodiment of the invention is as shown in Fig. 2, production lime, carbon dioxide, peace hydrogen production and electric power output are same When by-product coal ash and sulfur-bearing product, including rotary kiln 33, feed preheater 34, lime silo, reactor product cooler 36, raw material cabin, Fuel conduit, pure oxygen pipeline, waste heat power generation equipment 2, Ke Laipu unit 3, transformation separation equipment 4, carbon dioxide purification equipment 5, Harmful substance removal equipment 37 and peace hydrogen production unit 6.Rotary kiln is the rotary kiln for producing lime, and rotary kiln is equipped with feed inlet 31, discharge port and exhanst gas outlet, raw material cabin are connect by feed preheater with feed inlet, and discharge port is connected by reactor product cooler To lime silo.It is externally provided with carbon dioxide gas seal box in the static and dynamic sealing part flap connecting with kiln head cover, kiln hood, is sealed The pressure of case is higher than the kiln inner pressure of partition rotary kiln, guarantees that the gas in rotary kiln effectively completely cuts off with outside air.Coke powder combustion The functional gasification in burner of material and pure oxygen generates 1600 DEG C of high temperature, 900 DEG C of flue gases in rotary kiln after calcined limestone Through feed preheater, generates electricity after preheating material to waste heat power generation equipment 2, then remove titanium dioxide through harmful substance removal equipment Temperature is down to 300 DEG C after sulphur, a small amount of nitrogen oxides and dust, generates electricity into Ke Laipu unit.Leaving Ke Laipu cell temperature is 70 DEG C of flue gas converts carbon monoxide into carbon dioxide and hydrogen into transformation separation equipment 4, and isolates hydrogen and dioxy Change carbon.Ke Laipu unit is separated by cycle heat exchange medium pipeline 25 with peace hydrogen production unit 6, reactor product cooler 36 and transformation Equipment 4 is separately connected to form circulation loop, recycles the waste heat of these equipment: peace 6 magnesium system metal of hydrogen production unit inhales what hydrogen was released Heat；The sensible heat of high-temperature product after reactor product cooler 36 is calcined converts carbon monoxide in separation equipment 4 and reacts generation with vapor The chemical heat that carbon dioxide and hydrogen are released.Raw limestone, into lime rotary kiln 33, is forged after the preheating of feed preheater 34 Product discharges after entering the cooling of reactor product cooler 36 after the completion of burning, and other processes and operation are same as Example 1.
Embodiment 3
The third embodiment of the invention is as shown in figure 3, production clinker, carbon dioxide, peace hydrogen production and electric power are defeated Out simultaneously by-product coal ash and sulfur-bearing product, including rotary kiln 33, feed preheater 34, clinker storehouse, reactor product cooler 36, Raw material cabin, fuel conduit, pure oxygen pipeline, Ke Laipu unit 3, transformation separation equipment 4, carbon dioxide purification equipment 5, harmful substance Remove equipment 37 and peace hydrogen production unit 6.Rotary kiln is the rotary kiln for producing clinker, and rotary kiln is equipped with feed inlet, discharging Mouth and exhanst gas outlet, raw material cabin are connect by feed preheater with feed inlet, and discharge port is connected to cement by reactor product cooler Clinker storehouse.Carbon dioxide gas seal box, seal box are externally provided in the static and dynamic sealing part flap connecting with kiln head cover, kiln hood Pressure be higher than partition rotary kiln kiln inner pressure, guarantee rotary kiln in gas effectively completely cut off with outside air.Coke powder fuel Completely burned generates 1600 DEG C of height in rotary kiln burner with pure oxygen gaseous mixture (mixed proportion oxygen: carbon dioxide 30: 70) Temperature, 1050 DEG C of the flue gas in rotary kiln after calcining production clinker is through feed preheater, through nuisance after preheating material Temperature is down to 300 DEG C after matter removing equipment scrubbing CO_2, a small amount of nitrogen oxides and dust, sends out into Ke Laipu unit Electricity.Leaving Ke Laipu cell temperature is 70 DEG C of flue gas, into transformation separation equipment 4 convert carbon monoxide into carbon dioxide and Hydrogen, and isolate hydrogen and carbon dioxide.Purity oxygen and carbon dioxide mix ratio oxygen: carbon dioxide 99: 1, into original The burner of preheater 34 is expected as gasifying agent, and another way is conveying power wind with carbon dioxide, and conveying coke powder fuel enters burner Functional gasification is carried out, heating lime stone raw material carries out predecomposition, and the calorific intensity for increasing device improves yield.
The operational process of the clinker process units are as follows: cement raw material enter feed preheater 34 exchange heat after, into return The kiln thorax of rotary kiln, the lime product after the completion of calcining discharge after entering reactor product cooler cooling.Pure oxygen gaseous mixture (mixed proportion oxygen Gas: carbon dioxide 30: 70) completely burned generates 1600 DEG C of high-temperature flue gas based on carbon dioxide in rotary kiln burner, 1050 DEG C of flue gas in rotary kiln after calcining production clinker is through feed preheater, preheating material.Another operating condition is pure Oxygen gas mixture (mixed proportion oxygen: carbon dioxide 99: 1) and coke powder fuel carry out the cigarette of functional gasification in rotary kiln burner Gas is based on carbon monoxide and carbon dioxide.Purity oxygen and carbon dioxide mix ratio oxygen: carbon dioxide 99: 1, into raw material For the burner of preheater 34 as gasifying agent, another way is conveying power wind with carbon dioxide, conveying coke powder fuel enter burner into The functional gasification of row, heating lime stone raw material carry out predecomposition.Rotary kiln burner and feed preheater burner 46 can be single respectively It solely uses, rotary kiln and preheater burner 46 can also be replaced like that similar to Fig. 4 functionality gasification furnace 35.Feed preheater out Flue gas temperature after harmful substance removal equipment scrubbing CO_2, a small amount of nitrogen oxides and dust is down to 300 DEG C, into Ke Carry out the power generation of Pu unit.The flue gas that Ke Laipu cell temperature is 70 DEG C is left, is converted carbon monoxide into transformation separation equipment 4 Carbon dioxide and hydrogen, and isolate hydrogen and carbon dioxide.The carbon dioxide a part separated is set into carbon dioxide purification Standby 5, go out device as industrial grade carbon-dioxide after purification, a part to pure oxygen pipeline adjusts combustion-supporting gas oxygen content, with control Calcination temperature, some provides power wind to fuel pump deliver line for coke powder conveying.The circulating picture-changing of Ke Laipu unit connection The cycle heat exchange medium of heat medium pipeline 25 be heat exchange after low temperature exhaust gas, calcined by rotary kiln tail gas through Ke Laipu unit recycle more than After heat, part low temperature exhaust gas gives cycle heat exchange medium, and main component is carbon monoxide or carbon dioxide.Low-temperature circulating heat transferring medium It is come out from Ke Laipu unit, individually by peace hydrogen production unit 6, reactor product cooler 36, and transformation separation equipment 4, recycling After the waste heat heat exchange heating of these equipment, Ke Laipu unit is returned, heat is outer defeated to the power generation of Ke Laipu unit.Other processes and It operates same as Example 1.
Embodiment 4
4th kind of embodiment of the invention is as shown in figure 4, production calcium carbide calcium carbide, carbon dioxide, peace hydrogen production and electric power Output while by-product coal ash and sulfur-bearing product, including rotary kiln 33, feed preheater 34, functional gasification furnace 35, lime-ash are cold But device 47, carbide raw material storehouse, calcium carbide storehouse, fuel conduit, pure oxygen pipeline, Ke Laipu unit 3, reactor product cooler 36, transformation separation Equipment 4, carbon dioxide purification equipment 5, harmful substance removal equipment 37 and peace hydrogen production unit 6.Rotary kiln is zero-emission calcium carbide Rotary kiln, zero-emission calcium carbide rotary kiln is equipped with carbide raw material feed inlet and calcium carbide exports.It is dynamic what is connect with kiln head cover, kiln hood Static seal flap is externally provided with carbon dioxide gas seal box, and the pressure of seal box is higher than the kiln inner pressure of partition rotary kiln, Guarantee that the gas in zero-emission calcium carbide rotary kiln effectively completely cuts off with outside air.Fuel conduit and pure oxygen piping connection are to functionality Gasification furnace, functional gasification furnace are connected to the burner hearth of rotary kiln.The functional gasification in burner of coke powder fuel and pure oxygen generates 2300 DEG C of high temperature, 1300 DEG C of flue gases in rotary kiln after calcining production calcium carbide, preheats carbide raw material through feed preheater 34 Afterwards, 1000 DEG C of flue gas generates electricity through waste heat power generation equipment 2, then through harmful substance removal equipment scrubbing CO_2, a small amount of nitrogen Temperature is down to 300 DEG C after oxide and dust, generates electricity into Ke Laipu unit.Leave the cigarette that Ke Laipu cell temperature is 70 DEG C Gas converts carbon monoxide into carbon dioxide and hydrogen into transformation separation equipment 4, and isolates hydrogen and carbon dioxide.Electricity Stone arrives calcium carbide storehouse after reactor product cooler 36 is cooling.Ke Laipu unit passes through cycle heat exchange medium pipeline 25 and peace hydrogen production unit 6, reactor product cooler 36, ash-dregs cooler 47 and transformation separation equipment 4 are separately connected to form circulation loop, recycle these equipment Waste heat: peace 6 magnesium metal system metal of hydrogen production unit inhales the heat that hydrogen is released, the sensible heat of high-temperature product after reactor product cooler 36 is calcined And heat of solidification, the sensible heat and heat of solidification of 47 lime-ash of ash-dregs cooler, it converts carbon monoxide in separation equipment 4 and reacts life with vapor The chemical heat released at carbon dioxide and hydrogen.The cycle heat exchange medium of the cycle heat exchange medium pipeline 25 of Ke Laipu unit connection It is the low temperature exhaust gas after heat exchange, zero-emission calcium carbide calcined by rotary kiln tail gas is after Ke Laipu unit recovery waste heat, part low temperature tail Gas gives cycle heat exchange medium, and main component is carbon monoxide or carbon dioxide.Low-temperature circulating heat transferring medium goes out from Ke Laipu unit Come, individually recycles this by peace hydrogen production unit 6, reactor product cooler 36, and transformation separation equipment 4, ash-dregs cooler 47 After the waste heat heat exchange heating of a little equipment, Ke Laipu unit is returned, heat is outer defeated to the power generation of Ke Laipu unit.Functional gasification furnace Be it is a kind of by pure oxygen and coke powder in gasification furnace imperfect combustion generate a large amount of heat formed with carbon monoxide be mainly at The high-temperature mixed gas divided supplies next industrial furnace and carries out heating or reduction reaction or can also carry out protectiveness heating process Equipment, while the liquid lime-ash of fuel is discharged out of the furnace in functional gasification furnace.Other processes and operation and 3 phase of embodiment Together.
Embodiment 5
5th kind of embodiment of the invention is as shown in figure 5, the production pig iron, carbon dioxide, peace hydrogen production and electric power export, together When by-product coal ash and sulfur-bearing product, including rotary kiln 33, feed preheater 34, functional gasification furnace 35, ash-dregs cooler 47, Iron-smelting raw material storehouse, fuel conduit, pure oxygen pipeline, Ke Laipu unit 3, reactor product cooler 36, transformation separation equipment 4, carbon dioxide Equipment for purifying 5, harmful substance removal equipment 37 and peace hydrogen production unit 6.Rotary kiln is that the pig iron produces rotary kiln, and rotary kiln is equipped with Material inlet and pig iron outlet.To functional gasification furnace, functional gasification furnace is connected to for fuel conduit and pure oxygen piping connection The burner hearth of rotary kiln.The functional gasification in functional gasification furnace 35 of coke powder fuel and pure oxygen generates 2000 DEG C of high temperature, is returning 1000 DEG C of flue gases in rotary kiln after calcining production molten iron, after feed preheater 34 preheats pig iron raw material, more than 600 DEG C of flue gas warp Hot generating equipment 2 generates electricity, and then temperature drops after harmful substance removal equipment abjection sulfur dioxide, a small amount of nitrogen oxides and dust To 300 DEG C, generate electricity into Ke Laipu unit.The flue gas that Ke Laipu cell temperature is 70 DEG C is left, it will into transformation separation equipment 4 Carbon monoxide is converted to carbon dioxide and hydrogen, and isolates hydrogen and carbon dioxide.Molten iron is after reactor product cooler 36 is cooling To product storehouse.Iron-smelting raw material is one or more of with sponge iron, iron ore pellet, sinter, oxidation iron ore or iron oxide miberal powder For the raw material of main component.The other processes of the present embodiment are same as Example 4.
Embodiment 6
6th kind of embodiment of the invention is as shown in fig. 6, production active lime, carbon dioxide, peace hydrogen production and electric power are defeated Out simultaneously by-product coal ash and sulfur-bearing product, including beam type shaft furnace 7, fuel conduit, pure oxygen pipeline, carbon monoxide supplement pipeline, Reactor product cooler, flue gas heat-exchange unit 9, Ke Laipu unit 3, transformation separation equipment 4, carbon dioxide purification equipment 5, harmful substance are de- Except equipment 37, functional gasification furnace 35 and peace hydrogen production unit 6.Beam type shaft furnace is equipped with burning beam 8 and bottom gas cooled nozzle 29, burning beam is equipped with Heat-conduction oil circulation system 45, for cooling down beam body.The exhanst gas outlet of beam type shaft furnace passes through flue gas heat-exchange unit 9 It is divided into three tunnels with harmful substance removal equipment 37, is connected to carbon dioxide purification equipment 5 all the way, is connected to transformation separation all the way and sets Standby 4, it is carbon monoxide supplement piping connection all the way to bottom gas cooling spout 29, three tunnels are respectively equipped with valve.Purity oxygen with Carbon dioxide mix ratio oxygen: carbon dioxide 98: 2, entered function gasification furnace 35 are used as gasifying agent, and another way is with carbon dioxide To convey power wind, conveying coke powder entered function gasification furnace 35 carries out functional gasification, generates 1350 DEG C of high temperature, pass through burning Enter lime burning in limekiln along downward or two sides spout inside beam, then the flue gas of 350 DEG C of generation enters flue gas and changes Hot device 9, by being connect after harmful substance removal equipment 37 with transformation separation equipment 4.When pure oxygen mixture (mixing in burning beam 8 Ratio oxygen: carbon dioxide 25: when 75) carrying out completely burned generation carbon dioxide with coke powder, tail gas is led to based on carbon dioxide It crosses after harmful substance removal equipment 37 and walks dotted line and connect with carbon dioxide purification equipment 5, without using transformation separation equipment 4 and An Qing Production unit 6.The outlet of carbon dioxide purification equipment 5 is connected to technical grade or food-grade carbon-dioxide storage tank all the way, and another way connects It is connected to the combustion-supporting gas pipeline, fuel pump deliver line and bottom gas cooled nozzle of beam type shaft furnace, combustion-supporting gas pipeline, fuel are defeated It send pipeline to pass through functional gasification furnace 35 and is connected to burning beam 8.Burning beam passes through thermally conductive oil circuit piping 45 and Ke Laipu unit 3 Connection forms circulation loop, and to prevent burning beam overtemperature conduction oil cooling, cooling heat carrys out pump apparatus recycling power generation to Ke. 190 DEG C of conduction oils of high temperature of burning beam, which enter Ke Laipu unit and heat is transmitted to Ke carrys out pump apparatus, is reduced to the temperature of conduction oil 180 DEG C, the conduction oil of 180 DEG C of low temperature is delivered in burning beam again.Ke Laipu unit is divided by cycle heat exchange medium pipeline 25 Shape is not connect with flue gas heat-exchange unit 9, transformation separation equipment 4, peace hydrogen production unit 6, ash-dregs cooler 47 and reactor product cooler 36 At circulation loop, the waste heat of these equipment: the waste heat of 9 product tail gas of flue gas heat-exchange unit is recycled；Convert an oxidation in separation equipment 4 Carbon reacts the chemical heat for generating that carbon dioxide and hydrogen are released with vapor；Pacify magnesium system metal in hydrogen production unit 6 and inhales hydrogen releasing Heat；The sensible heat and condensation heat of 47 lime-ash of ash-dregs cooler；The sensible heat of 36 high-temperature product of reactor product cooler.Functional gasification furnace 35 can be used alone, can also similar Fig. 3 feed preheater burner 46 functional gasification furnace 35 of replacement like that, coke powder and pure oxygen Gaseous mixture goes out and lights from downward and two side sprays of burning beam, brings coke powder ash content into product.When pure oxygen gaseous mixture in burner 46 When (mixed proportion oxygen: carbon dioxide 25: 75) and coke powder carry out completely burned generation carbon dioxide, tail gas is with carbon dioxide It is main, it is connect by walking dotted line after harmful substance removal equipment 37 with carbon dioxide purification equipment 5, without using transformation separation equipment 4 With peace hydrogen production unit 6.When pure oxygen gaseous mixture (mixed proportion oxygen: carbon dioxide 50: 50) in burner 46 and coke powder carry out function Can property gasification when generating carbon monoxide, tail gas is based on carbon monoxide and carbon dioxide, by harmful substance removal equipment 37, into It is divided into two tunnels after entering to convert separation equipment 4, is connected to carbon dioxide purification equipment 5 all the way, is connected to peace hydrogen production unit all the way 6.Burning beam 8 can be multilayer, every layer can be more, 8 bottom of burning beam and dual side-edge can have nozzle.Functionality gasification Furnace 35 or burner 46 can be separately provided according to burning beam can also concentrated setting.Bottom gas cooled nozzle 29 and reactor product cooler 36, it can be set simultaneously or individually.The other processes of the present embodiment and operation are same as Example 5.
Embodiment 7
7th kind of embodiment of the invention is as shown in fig. 7, production active lime, carbon dioxide, peace hydrogen production and electric power are defeated Out, including double-hearth lime kiln 10, flue gas heat-exchange unit 9, fuel conduit, carbon monoxide supplement pipeline, pure oxygen pipeline, Ke Laipu unit 3, separation equipment 4, carbon dioxide purification equipment 5, harmful substance removal equipment 37 and peace hydrogen production unit 6 are converted.Double thorax lime Kiln is equipped with fuel (conveying coke powder by tail gas carbon dioxide air-flow) import 28 and bottom gas cooled nozzle 29.Double-hearth lime kiln Exhanst gas outlet three tunnels are divided by flue gas heat-exchange unit 9 and harmful substance removal equipment, be connected to carbon dioxide purification all the way and set Standby 5, it is connected to transformation separation equipment 4 all the way, is that carbon monoxide supplements piping connection to bottom gas cooling spout 29 all the way, three Road is respectively equipped with valve.The carbon dioxide outlet of transformation separation equipment is connected to carbon dioxide purification equipment 5 all the way, and another way connects It is connected to bottom gas cooled nozzle 29 and the fuel inlet 28 of double-hearth lime kiln.The flue-gas temperature of double-hearth lime kiln exhanst gas outlet is 150 DEG C, 70 DEG C are reduced to after the heat exchange of flue gas heat-exchange unit 9.Ke Laipu unit by cycle heat exchange medium pipeline 25, respectively with flue gas Heat exchanger 9, transformation separation equipment 4, peace hydrogen production unit 6 and the connection of reactor product cooler 36 form circulation loop, recycle these and set Standby waste heat: the waste heat of the calcining production product tail gas of flue gas heat-exchange unit 9；It is anti-to convert carbon monoxide and vapor in separation equipment 4 The chemical heat that carbon dioxide and hydrogen are released should be generated；Pacify magnesium system metal in hydrogen production unit 6 and inhales the heat that hydrogen is released；Product is cold But the product sensible heat of high temperature after device 36 is calcined.Fuel is that coke powder is conveyed with carbon dioxide, into more sprays inside double thorax kilns Rifle, pure oxygen mixed proportion oxygen: carbon dioxide 50: 50 carries out functional gasification in burner hearth, and tail gas main component is an oxidation The mixture of carbon and carbon dioxide.It is defeated outside Ke Laipu unit electricity to be connected to the grid.Another situation, fuel are coke powders with two Carbonoxide conveying, into more spray guns inside double thorax kilns, pure oxygen mixed proportion oxygen: carbon dioxide 25: 75, it is complete in burner hearth Full burning, tail gas main component is carbon dioxide.It is set by walking dotted line after harmful substance removal equipment 37 with carbon dioxide purification Standby 5 connection, without using transformation separation equipment 4 and peace hydrogen production unit 6.The other processes of the present embodiment and operation and 6 phase of embodiment Together.
Embodiment 8
8th kind of embodiment of the invention is as shown in figure 8, production active lime, carbon dioxide, peace hydrogen production and electric power are defeated Out, including sleeve kiln 44, flue gas heat-exchange unit 9, fuel conduit, carbon monoxide supplement pipeline, pure oxygen pipeline, Ke Laipu unit 3, become Change separation equipment 4, carbon dioxide purification equipment 5, harmful substance removal equipment 37 and peace hydrogen production unit 6.Sleeve kiln is equipped with upper The functional gasification burner tip 30 of lower two row 14, top feed mouth 31 and bottom gas cooled nozzle 29,14 functional gasifications are burnt Mouth is uniformly distributed around sleeve kiln cylinder body.The exhanst gas outlet of sleeve kiln passes through flue gas heat-exchange unit 9 and harmful substance removal equipment point Cheng Sanlu, is connected to carbon dioxide purification equipment 5 all the way, is connected to transformation separation equipment 4 all the way, is carbon monoxide supplement all the way For piping connection to bottom gas cooling spout 29, three tunnels are respectively equipped with valve.Convert the carbon dioxide outlet of separation equipment all the way It is connected to carbon dioxide purification equipment 5, another way is connected to the bottom gas cooled nozzle 29 of sleeve kiln and functional gasification is burnt Mouth 30.Fuel is that coke powder is conveyed with carbon dioxide, entered function gasification burner tip 30, pure oxygen mixed proportion oxygen: titanium dioxide Carbon 50: 50 carries out functional gasification in functional gasification burner tip 30, and tail gas main component is carbon monoxide and carbon dioxide Mixture.Another situation, fuel are that coke powder is conveyed with carbon dioxide, entered function gasification burner tip 30, pure oxygen mixing ratio Example oxygen: carbon dioxide 25: 75, the completely burned in burner hearth, tail gas main component are carbon dioxide.Pass through harmful substance removal It walks dotted line after equipment 37 to connect with carbon dioxide purification equipment 5, without using transformation separation equipment 4 and peace hydrogen production unit 6.Ke Lai Pu unit by cycle heat exchange medium pipeline 25, respectively with flue gas heat-exchange unit 9, transformation separation equipment 4, peace hydrogen production unit 6 and The connection of reactor product cooler 36 forms circulation loop, recycles the waste heat of these equipment: the calcining production product tail gas of flue gas heat-exchange unit 9 Waste heat；Carbon monoxide reacts the chemical heat for generating that carbon dioxide and hydrogen are released with vapor in transformation separation equipment 4；It is raw to pacify hydrogen It produces magnesium system metal in unit 6 and inhales the heat that hydrogen is released；The sensible heat of high-temperature product after reactor product cooler 36 is calcined.Ke Laipu unit hair Electricity outer defeated be connected to the grid.The other processes of the present embodiment and operation are same as Example 7.
Embodiment 9
9th kind of embodiment of the invention is as shown in figure 9, the production pig iron, carbon dioxide, peace hydrogen production and electric power output, packet Include blast furnace 32, Differential pressure power generation equipment 39, flue gas heat-exchange unit 9, reactor product cooler 36, coke powder pipeline, pure oxygen pipeline, Ke Laipu Unit 3, transformation separation equipment 4, carbon dioxide purification equipment 5, harmful substance removal equipment 37 and peace hydrogen production unit 6.Ironmaking Blast furnace is equipped with burner 46, molten iron outlet and feed inlet 31, burner and fuel conduit and pure oxygen piping connection.Blast furnace flue gas goes out Mouth is connected to harmful substance removal equipment 37 by Differential pressure power generation equipment 39 and flue gas heat-exchange unit 9, and tail gas first carries out Differential pressure power generation It exchanges heat again.Transformation separation is connected to after harmful substance removal equipment scrubbing CO_2, a small amount of nitrogen oxides and dust to set Standby 4, two tunnels of carbon dioxide outlet point of transformation separation equipment 4 are connected to carbon dioxide purification equipment 5 all the way, are connected to all the way Pure oxygen pipeline and coke powder transfer pipeline, hydrogen outlet are connected to peace hydrogen production unit 6.The effect for converting separation equipment 4 is by tail Carbon monoxide in gas reacts production carbon dioxide and hydrogen with water.Blast furnace air inlet adds carbon dioxide, fuel coke powder using oxygen Deliver into burner 46 with carbon dioxide, pure oxygen mixed proportion oxygen: carbon dioxide 70: 30 carries out functional in burner 46 Gasification, to generate a large amount of carbon monoxide and the carbon dioxide there are part, blast furnace tail gas main component be carbon dioxide and Carbon monoxide.Tail gas first carries out Differential pressure power generation and exchanges heat again.Harmful substance removal equipment scrubbing CO_2, a small amount of nitrogen oxidation Object and dust.The outlet setting carbon monoxide of harmful substance removal equipment 37 supplements pipeline, and carbon monoxide supplement piping connection arrives Coke powder pipeline, supplementing pipeline to enter the gas gross of blast furnace 32 by carbon monoxide is by coke powder pipeline and pure oxygen pipeline Into the 30%-50% of the total carbon dioxide capacity in blast furnace 32, for improving the atmosphere in kiln thorax, it is more reasonable to make to be distributed, Combustion efficiency is good, guarantees product quality, obtains good economic effect.Ke Laipu unit passes through cycle heat exchange medium pipeline 25, It connect with flue gas heat-exchange unit 9, transformation separation equipment 4, peace hydrogen production unit 6 and reactor product cooler 36 respectively and to form circulation loop, Recycle the waste heat of these equipment: the waste heat of 9 tail gas of flue gas heat-exchange unit；Carbon monoxide is reacted with vapor in transformation separation equipment 4 Generate the chemical heat that carbon dioxide and hydrogen are released；Pacify magnesium system metal in hydrogen production unit 6 and inhales the heat that hydrogen is released；Product is cooling The sensible heat and condensation heat of high-temperature product after device 36 is calcined.Ke Laipu unit electricity and 39 electricity of Differential pressure power generation equipment individually or It is in parallel outer defeated.The other processes of the present embodiment and operation it is same as Example 8, unlike harmful substance removal equipment 37 outlet with It converts separation equipment 4 to connect, the pipeline not being directly connected to carbon dioxide purification equipment 5.
Pure oxygen pipeline in above-described embodiment 1-9 can be substituted by oxygen-enriched pipeline, and combustion-supporting gas is oxygen-enriched and carbon dioxide Gaseous mixture, mixed proportion be 0:100~100:0(volume ratio), nitrogen and nitrogen oxides are by subsequent harmful substance removal Equipment 37 removes.
Embodiment 10
Tenth kind of embodiment of the invention is as shown in figure 13, production active lime, carbon dioxide product and it is outer for electric power and Combustion gas, while by-product coal ash and sulfur-bearing product, including partition rotary kiln 1, shaft furnace 55, raw limestone storehouse 20, lime silo, production Product cooler 36, Ke Laipu unit 3, carbon dioxide purification equipment 5, coal dust pipeline and pure oxygen pipeline.Partition rotary kiln is as implemented The structure of example 1 is four-part form partition rotary kiln, and combustion apparatus is burner 46, and each section is respectively equipped with feed inlet, discharge port, partition Tonifying Qi entrance 24 and decomposed gas outlet 21 are calcined, partition rotary kiln is equipped with exhanst gas outlet, fuel lime-ash outlet 38.Decompose gas 21 connection carbon dioxide purification equipment 5 of outlet, carbon dioxide purification equipment 5 connect carbon dioxide finished pot 49.
The burner of coal dust pipeline and pure oxygen piping connection partition rotary kiln, coal dust pipeline use air as conveying gas, Air also can be used as diluent in pure oxygen pipeline, is mixed into oxygen rich gas supply burner, the exhanst gas outlet of partition rotary kiln connects The bottom of logical shaft furnace 55, shaft furnace connects lime product storehouse by reactor product cooler 36, and the exhanst gas outlet at the top of shaft furnace passes through air inducing It is divided into two-way after machine, connects gas collection tank all the way, store for future use；Another way leads back shaft furnace bottom as cooling gas.
Ke Laipu unit by cycle heat exchange medium pipeline 25, respectively with bulk lime silo 11, middle lump lime storehouse 12, fritter The connection of reactor product cooler 36 of lime silo 13, powder lime silo 14, shaft furnace forms circulation loop, recycles the waste heat of these equipment: Four lime silo high temperature product sensible heats, the product sensible heat of 36 high temperature of reactor product cooler.
The operational process of the present embodiment are as follows: the lime stone in raw limestone storehouse 20 is sent through conveying equipment to classification feeder 19, according to grade classification respectively through bulk feed inlet 15, middle piece of feed inlet 16, fritter feed inlet 17 and powder feed inlet 18, with After the heat exchange of calcining and decomposing gas high temperature carbon dioxide, into the annular materials space of each section of partition rotary kiln.Coal dust is by air wind-force Conveying, oxygen-enriched and coal dust carry out functional gasification in burner combustion, and functionality gasification is exactly that raw material coal dust and gasifying agent pure oxygen exist Imperfect combustion generates carbon monoxide and a small amount of other gases in partition rotary kiln, and when gasification can add partial CO 2 gas As diluent；And the multiple functions of lime calcining, temperature control and deslagging are realized while completing gasification.Gasification temperature is 1430 DEG C, the limestone material in each section of annular materials space of partition rotary kiln is calcined, lime enters the production of each grade through each discharge port Product storehouse.The decomposition gas generated in calcination process is mentioned through each section of decomposed gas outlet 21 into carbon dioxide purification equipment 5 It is pure.The temperature of calcined kiln exit gas is up to 1000 DEG C and enters shaft furnace.Decomposition of limestone in shaft furnace is lime, and lime passes through Lime silo is collected into after reactor product cooler.Flue gas at the top of shaft furnace is collected into gas cooling tank as fuel and stores for future use, separately Extension gas is passed through shaft furnace bottom coohng lime.
The present embodiment midfeather channel can also be passed through any other material, such as be used to smelt iron, carbonization of coal.When being used for When carbonization of coal, it is passed through coal dust in the partition channel of partition rotary kiln, the decomposition gas after pulverized coal coking is by decomposed gas outlet 21 After extraction, the kiln hood end where being introduced back the burner of partition rotary kiln enters kiln thorax adjustment atmosphere.Allow in raw limestone Carbonaceous material is added, increases CO2The calorific value of gas when discharge.
Embodiment 11
Tenth a kind of embodiment of the invention is as shown in figure 16, produces coke, coke powder, active lime, calcining and decomposing gas Product is simultaneously outer for electric power and combustion gas, while by-product coal ash and sulfur-bearing product.Device includes partition rotary kiln 1, shaft furnace 55, lime Storehouse, reactor product cooler 36, Ke Laipu unit 3, coal dust pipeline and pure oxygen pipeline.Partition rotary kiln 1 produces coal for coal carbonization Gas, coke powder and coke, shaft furnace produce lime for calcined limestone.The structure phase of 1 partition rotary kiln of partition rotary kiln embodiment It together, is four-part form partition rotary kiln, combustion apparatus is burner 46.Partition rotary kiln is equipped with exhanst gas outlet, fuel lime-ash outlet 38, Each section is respectively equipped with feed inlet, discharge port and decomposed gas outlet 21.Bulk lime silo 11, middle lump lime storehouse 12, small lump lime Storehouse 13 and powder lime silo 14 are changed to bulk coke powder storehouse, middle piece of coke powder storehouse, nut coke powder cabin and powder coke powder storehouse, raw limestone Storehouse 20 is changed to pulverized coal bin, and classification feeder 19 is changed to coal dust feeder.Decomposed gas outlet 21 is connected to burner 46, coke powder/coke The outlet of charcoal is connected to burner all the way.
The burner of coal dust pipeline and pure oxygen piping connection partition rotary kiln, coal dust pipeline use air as conveying gas, Air also can be used as diluent in pure oxygen pipeline, is mixed into oxygen rich gas supply burner, the exhanst gas outlet of partition rotary kiln connects The bottom of logical shaft furnace 55, shaft furnace connects lime product storehouse by reactor product cooler 36, and the exhanst gas outlet at the top of shaft furnace passes through air inducing It is divided into two-way after machine, connects gas collection tank all the way, store for future use.Another way leads back shaft furnace bottom as cooling gas.Ke Lai Pu unit by cycle heat exchange medium pipeline 25, respectively with the reactor product cooler in the coal dust of partition rotary kiln (coke) storehouse and shaft furnace 36 connections form circulation loop, recycle the waste heat of these equipment.
The operational process of the present embodiment are as follows: the coal dust in pulverized coal bin is through defeated cuttings conveyer and calcining and decomposing gas converting heat Afterwards, the annular materials space for entering each section of partition rotary kiln through each section of feed inlet respectively carries out destructive distillation.Coal dust is by air wind-force Conveying, oxygen-enriched and coal dust carry out functional gasification in burner combustion, and functionality gasification is exactly that raw material coal dust and gasifying agent pure oxygen exist Imperfect combustion generates carbon monoxide and a small amount of other gases in partition rotary kiln, and when gasification can add partial CO 2 gas As diluent, and multiple functions of the realization to the destructive distillation of coal dust, temperature control and deslagging while completing gasification.Gasification temperature is 1430 DEG C, the coal dust in each section of annular materials space of partition rotary kiln, coke or coke powder are heated through each discharge port and enters each product Storehouse, coke powder enters burner 46 all the way, and the kiln hood end where being introduced back the burner of partition rotary kiln enters kiln thorax adjustment atmosphere.Calcining The coal gas generated in the process arrives the burner 46 of partition rotary kiln through each section of decomposed gas outlet 21.Calcined kiln exit gas Temperature is up to 1000 DEG C and enters shaft furnace.Decomposition of limestone in shaft furnace is lime, and lime is collected into after passing through reactor product cooler Lime silo.Flue gas at the top of shaft furnace is collected into gas cooling tank as fuel and stores for future use, and another extension gas is passed through shaft furnace Bottom coohng lime.

Claims (12)

1. a kind of commercial plant of zero-emission, including industrial furnace, raw material cabin, product storehouse, fuel conduit and combustion-supporting pipeline, described Industrial furnace is equipped with combustion apparatus, feed inlet (31), discharge port, reactor product cooler (36) and exhanst gas outlet, and the raw material cabin connects It is connected to feed inlet, the discharge port is connected to product storehouse by reactor product cooler, it is characterized in that: described device is equipped with power generation list Member, harmful substance removal equipment (37), Ke Laipu unit (3), transformation separation equipment (4) and carbon dioxide purification equipment (5), institute Stating Ke Laipu unit includes expanding machine (22), generator (23), hydrogen heat compression device (26) and resuperheater (27)；It is described Expander outlet is connected to expander inlet by hydrogen heat compression device, and the expanding machine is connect with generator shaft, the hair Motor is connect with external power circuit system；Described device is additionally provided with feed preheater (34) or flue gas heat-exchange unit (9), the combustion Burning equipment is burner (46), spray gun or the burning beam being mounted in stove, or the functional gasification furnace (35) being separately provided, institute It states functional gasification furnace and is provided with the burner (46), coal ash cooler (47) and tail gas of fuel conduit and combustion-supporting pipeline Mouthful, fuel and combustion-supporting gas carry out functional gasification in the burner hearth or functional gasification furnace of industrial furnace, generate with an oxidation Gas mixture based on carbon；The exhanst gas outlet of the industrial furnace connects harmful substance removal equipment by feed preheater (37), harmful substance removal equipment (37) are perhaps connected by feed preheater, generator unit or passes through flue gas heat-exchange unit (9) harmful substance removal equipment (37) are connected, or harmful substance removal equipment is connected by generator unit, flue gas heat-exchange unit (37)；The harmful substance removal equipment (37) is directly connected to or by Ke Laipu unit (3) connection transformation separation equipment (4), transformation separation equipment (4) is equipped with hydrogen outlet and carbon dioxide outlet, and the hydrogen outlet is connected to peace hydrogen production unit (6), the carbon dioxide outlet be connected to carbon dioxide purification equipment (5), combustion apparatus fuel conduit fuel conveying gas Entrance and combustion-supporting pipeline, the carbon dioxide purification equipment export are connected to food-grade or industrial grade carbon-dioxide finished pot (49)；Ke Laipu unit (3) passes through circulatory mediator pipeline and flue gas heat-exchange unit (9), product storehouse/product storehouse cooler, transformation point It is separately connected to form circulation loop from equipment (4), peace hydrogen production unit (6), coal ash cooler (47)；The generator unit is Waste heat power generation equipment (2) or/and differential pressure power generation equipment (39), the generator unit and Ke Laipu unit parallel power export or list Solely output.
2. the commercial plant of zero-emission according to claim 1, it is characterized in that: the harmful substance removal equipment (37) with Convert between separation equipment (4) or be arranged between the Ke Laipu unit (3) and transformation separation equipment (4) connection titanium dioxide The branch of carbon equipment for purifying (5).
3. the commercial plant of zero-emission according to claim 1, it is characterized in that: the industrial furnace includes blast furnace (32), rotary kiln (33), beam type shaft furnace (7), sleeve kiln (44) or double-hearth lime kiln (10), the rotary kiln include clinker Rotary kiln, zero-emission calcium carbide rotary kiln, ironmaking rotary kiln or coking of coal rotary kiln；The generator unit is waste heat power generation equipment (2) or differential pressure power generation equipment (39).
4. the commercial plant of zero-emission according to claim 1 or 2, it is characterized in that: the industrial furnace is equipped with raw material The rotary kiln of preheater (34), combustion apparatus are burner, in the static and dynamic sealing part flap peripheral hardware connecting with kiln head cover, kiln hood Have carbon dioxide gas seal box (48), the pressure of seal box is higher than the kiln inner pressure of rotary kiln, the exhanst gas outlet of industrial furnace It is connect afterwards with Ke Laipu unit (3) by feed preheater, waste heat power generation equipment (2), harmful substance removal equipment (37), Ke Lai Pu unit (3) connection transformation separation equipment (4), outlet connection carbon dioxide purification equipment (5) and peace of transformation separation equipment (4) Hydrogen production unit (6), Ke Laipu unit (3) pass through circulatory mediator pipeline and product storehouse/product storehouse cooler, transformation separation equipment (4), peace hydrogen production unit (6) is separately connected to form circulation loop；When the combustion-supporting gas and fuel progress functionality in rotary kiln When gasification reaction generates the gas mixture based on carbon monoxide, tail gas is separated afterwards with transformation by Ke Laipu unit (3) and is set Standby (4) connect, and tail gas is former by the chemical industry that can also be directly output as carbon mono oxide mixture after Ke Laipu unit (3) at this time Material or gaseous fuel；When tail gas gasifies as gaseous fuel in use, combustion-supporting gas can be used air as, gas fires Material is the gaseous mixture containing carbon monoxide, nitrogen and carbon dioxide；The burner of rotary kiln can be arranged separately in inside kiln body, It can be substituted by functional gasification furnace (35), when functional gasification furnace is arranged, Ke Laipu unit (3) also passes through circulatory mediator pipe Road connect to form circulation loop with coal ash cooler (47)；Fuel is carried out by carbon dioxide wind model by burner combustion Functionality gasification, functionality gasification are exactly that fuel and gasifying agent pure oxygen/oxygen-enriched imperfect combustion in rotary kiln generate an oxidation Carbon and a small amount of other gases, when gasification, add partial CO 2 gas as diluent, and realize while completing and gasifying The multiple functions of lime calcining, temperature control and deslagging；When combustion-supporting gas is the oxygen-enriched gaseous mixture with carbon dioxide, by harmful substance It removes equipment (37) and removes extra nitrogen and N-oxide impurity；Pure oxygen/oxygen-enriched the volume ratio with carbon dioxide mix gas It is 0: 100~100: 0；When rotary kiln is partition rotary kiln (1), partition rotary kiln (1) kiln body is tube-in-tube structure, by same The inner cylinder (50) and outer cylinder (54) of axis installation are constituted, and the center of inner cylinder is kiln thorax (51), are material channel between inner barrel and outer barrel (53), the material channel, which is equipped with, supports resistance to material (52)；Partition rotary kiln fuel, will by partition-wall heat transfer in intermediate hearth combustion Heat transfer is calcined to the raw material in annular space, since the continuous rotation of partition rotary kiln makes material thermally equivalent, and And slowly flowed from feed end to discharge end, it discharges after the completion of calcining；Combustion space is separated with calcination space, can be produced high-purity The high-quality product that degree is not heated by smoke pollution isolation air；Functional gasification furnace is a kind of by pure oxygen/oxygen-enriched and dioxy It is as main component with carbon monoxide to change a large amount of heat formation of carbon gaseous mixture and fuel the imperfect combustion generation in gasification furnace High-temperature mixed gas supplies next industrial furnace and carries out heating or reduction reaction or can also carry out setting for protectiveness heating process It is standby, while the liquid lime-ash of fuel is discharged out of the furnace in functional gasification furnace.
5. the commercial plant of zero-emission according to claim 4, it is characterized in that: the partition rotary kiln (1) is according to temperature Degree section is at least divided into one section of segmented partition rotary kiln, is equipped with raw limestone storehouse (20), classification feeder (19), partition Each section of rotary kiln (1) is respectively equipped with feed inlet, discharge port, partition calcining tonifying Qi entrance (24) and decomposed gas outlet (21)；Institute It states raw limestone storehouse (20) and is connected to classification feeder (19), classification feeder is connected to classification feed inlet, each discharging Mouth is connected to each classification lime silo；Each section of decomposed gas outlet is connected to carbon dioxide purification equipment (5)；The partition returns Rotary kiln is equipped with fuel lime-ash outlet (38)；Rotary kiln burner (46) carries out functional gasification, and rotary kiln burner (46) can also be used Individual device functionality gasification furnace (35) replaces, and enters partition rotary kiln to generate the mixed gas based on high temperature carbon monoxide Kiln thorax；In functionality gasification, the Ke Laipu unit is connected to partition calcining tonifying Qi entrance, and calcined by rotary kiln tail gas is through Ke After carrying out Pu unit recovery waste heat, for extraction section low temperature exhaust gas to lime burning tonifying Qi to enhance product performance, air compensation is lime Stone calcining generates the 0~100% of tail gas amount.
6. the commercial plant of zero-emission according to claim 4, it is characterized in that: the rotary kiln is clinker revolution Burner is arranged in kiln, the feed preheater, and burner connects fuel conduit and combustion-supporting pipeline, and fuel and combustion-supporting gas are in raw material preheating Functional gasification is carried out in device, generates the gas mixture based on carbon monoxide；Or function is set up outside feed preheater Property gasification furnace, the offgas outlet of functional gasification furnace are connected to feed preheater.
7. the commercial plant of zero-emission according to claim 1 or 2, it is characterized in that: the industrial furnace is equipped with flue gas Bottom is arranged in the bottom of beam type shaft furnace (7), sleeve kiln (44) or the double-hearth lime kiln (10) of heat exchanger (9), the industrial furnace The exhanst gas outlet of gas cooling spout (29), industrial furnace is connected by flue gas heat-exchange unit (9), harmful substance removal equipment (37) It converts separation equipment (4), outlet connection carbon dioxide purification equipment (5) of transformation separation equipment (4) and peace hydrogen production unit (6), setting is connected to carbon dioxide purification equipment (5) between harmful substance removal equipment (37) and transformation separation equipment (4) Branch, the carbon monoxide supplement pipeline for being connected to bottom gas cooled nozzle (29)；Ke Laipu unit (3) passes through circulatory mediator pipe Road is separately connected to be formed and follow with flue gas heat-exchange unit (9), product storehouse cooler, transformation separation equipment (4), peace hydrogen production unit (6) Loop back path；It is mixed that combustion-supporting gas and fuel in industrial furnace carry out the gas that functional gasification reaction generates based on carbon monoxide When closing gas, tail gas is connect with transformation separation equipment (4) afterwards by harmful substance removal equipment (37), and tail gas passes through nuisance at this time The industrial chemicals or gaseous fuel of carbon mono oxide mixture can also be directly output as after matter removing equipment (37)；Industrial furnace Combustion apparatus can be arranged separately in inside kiln body, can also be substituted by functional gasification furnace, when functional gasification furnace is arranged When, Ke Laipu unit (3) also connect to form circulation loop by circulatory mediator pipeline with coal ash cooler (47)；Fuel is by two Carbonoxide wind model carries out functional gasification by burner combustion, and functionality gasification is exactly fuel and gasifying agent pure oxygen/oxygen-enriched Carbon monoxide and a small amount of other gas are generated in beam type shaft furnace (7), sleeve kiln (44) or the interior imperfect combustion of double-hearth lime kiln (10) Body adds partial CO 2 gas when gasification as diluent；And complete gasification while realize lime calcining, temperature control and The multiple functions of deslagging；It is de- by harmful substance removal equipment (37) when combustion-supporting gas is the oxygen-enriched gaseous mixture with carbon dioxide Except extra nitrogen and N-oxide impurity；Pure oxygen/oxygen-enriched volume ratio with carbon dioxide mix gas is 0: 100~100: 0.
8. the commercial plant of zero-emission according to claim 7, it is characterized in that: the industrial furnace is beam type shaft furnace (7), Beam type shaft furnace (7) is equipped with burning beam (8), and nozzles downward or to two sides are arranged in burning beam, are passed through cooling in burning beam Conduction oil, conduction oil connect to form circulation loop by thermally conductive oil circuit piping (45) with Ke Laipu unit (3), the height of burning beam Warm conduction oil, which enters Ke Laipu unit and heat is transmitted to Ke carrys out pump apparatus, reduces the temperature of conduction oil, again by the conduction oil of low temperature It is delivered in burning beam.
9. the commercial plant of zero-emission according to claim 1, it is characterized in that: the industrial furnace is equipped with flue gas heat exchange The blast furnace (32) of device (9), the exhanst gas outlet of blast furnace (32) by differential pressure power generation equipment (39), flue gas heat-exchange unit (9), Harmful substance removal equipment (37) is divided into two-way, all the way connection transformation separation equipment (4), another way by blast furnace into Preset air inlet is directly entered kiln thorax around air port；Convert the hydrogen outlet connection peace hydrogen production unit of separation equipment (4) (6), the carbon dioxide outlet for converting separation equipment (4) is divided into three tunnels, is connected to carbon dioxide purification equipment (5) all the way, all the way It is connected to fuel conduit, another way is connected to combustion-supporting pipeline；Ke Laipu unit (3) passes through circulatory mediator pipeline and flue gas heat-exchange unit (9), product storehouse cooler, transformation separation equipment (4), peace hydrogen production unit (6) are separately connected to form circulation loop.
10. the commercial plant of zero-emission according to claim 1, it is characterized in that: the hydrogen heat compression device (26) is set There are 2~100 groups of metal hydride reaction beds, the metal hydride reaction bed absorbs low pressure hydrogen at low temperature, at high temperature Release high pressure hydrogen；2~100 groups of metal hydride reaction beds are arranged to one or more levels, when being set as level-one, in peer The suction hydrogen temperature of metal hydride reaction bed is identical, and hydrogen discharging temperature is also identical；When being set as multistage, every grade of at least 2 groups of metals Hydride reaction bed, the hydrogen discharging temperature of upper level metal hydride reaction bed are higher than the hydrogen discharging temperature of next stage metal hydride, Upper level inhales suction hydrogen temperature of the hydrogen temperature also above next stage, and upper level metal hydride reaction bed inhales the heat released when hydrogen It supplies next stage metal hydride reaction bed to use, realizes the cascade utilization of heat；The expanding machine (22) is multiple expansion engine, Every level-one is equipped with bleeding point and air inlet, and the outlet port of upper level is connected to the air inlet of next stage by resuperheater (27) Mouthful；Ke Laipu unit adds hydrogen storage material tank and gating system, by between strength, fluid power or mechanical system realization grade or any two in grade Metal hydrogen storage material mutually switches between a metal hydride reaction bed；The Ke Laipu unit can add Organic Rankine Cycle Low-temperature cogeneration device, further increases efficiency；ORC (organic Rankine cycle) low-temperature device for generating power by waste heat includes evaporator (58), swollen Swollen machine (22), condenser (56), working medium pump (57) and generator (23), using low-boiling-point organic compound as working medium；Evaporator (58) outlet is connected to expanding machine (22) entrance, and expanding machine (22) outlet is connected to condenser (56) entrance, and condenser (56) goes out Mouth is connected to evaporator (58) entrance, expanding machine (22) and generator (23) axis connection by working medium pump (57)；Organic Rankine follows The expanding machine and original expanding machine of ring low-temperature cogeneration device, generator are independently arranged, or original with Ke Laipu unit Expanding machine and generator are shared or coaxial；If it is the latter, the cooling capacity for the cooling medium that condenser (56) uses can be hydrogen Cooling capacity or atmospheric environment or cooling water that gas expansion generates or the cooling capacity that other cold sources generate；Heat needed for evaporator (58) comes The low temperature exhaust heat of the heat and flue gas released when inhaling hydrogen from metal hydride reaction bed.
11. the commercial plant of zero-emission according to claim 1, it is characterized in that: the peace hydrogen production unit (6), including At least two hydrogen abstraction reaction devices (40), metal hydride more changing device (41), weary metal hydride container (42) and saturation gold Belong to hydride container (43)；The weary metal hydride container (42) is equipped with the metal discharged after hydrogen by metal hydride Hydrogen storage material, saturation metal hydride container (43), which is equipped with, absorbs the metallic hydrogen formed after hydrogen by metal hydrogen storage material Compound, the hydrogen abstraction reaction device metal hydride outlet by metal hydride more changing device respectively with weary metal hydride collection It cases (42) and saturation metal hydride container (43) connection, the metal hydride more changing device (41) passes through strength, liquid Power or mechanical system complete the interior metal hydrogen storage material of weary metal hydride container (42) and enter hydrogen abstraction reaction device (40) and inhale Metal hydrogen storage material in hydrogen reactor (40) absorbs the metal hydride formed after hydrogen and enters saturation metal hydride packaging The material transfer process of case (43)；The hydrogen abstraction reaction device is connected by cycle heat exchange medium pipeline (25) and Ke Laipu unit (3) It connects to form circulation loop, metal hydrogen storage material hydrogen abstraction reaction process releases a large amount of heat in hydrogen abstraction reaction device, by cycle heat exchange Cycle heat exchange medium indirect heat exchange in medium pipeline (25) is taken out of, and heat exchange generates electricity to Ke Laipu unit (3), which is situated between Matter may be hydrogen, and the heat that hydrogen abstraction reaction process is released is taken in directly heat exchange out of, and heat exchange gives Ke Laipu unit (3) to generate electricity；By When in use, the releasing of hydrogen uses following either type to the magnesium system metal hydride of peace hydrogen production unit (6) production: first is that Hydrogen is released after magnesium system metal hydride is heated to set temperature；Second is that addition water or water vapour conduct help while heating Hydrogen is released in agent；Third is that after hydrogen release of the heated progress of magnesium system metal hydride is decomposed into magnesium simple substance, then fill into water or water steaming Vapour is reacted with magnesium simple substance generates the secondary hydrogen release of hydrogen progress.
12. the commercial plant of zero-emission according to claim 1, it is characterized in that: stone can be used when product is fuel gas The cooling system that ash furnace makees functional gasification reduces temperature, while making to produce the device of lime.
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