CN109983102A - The minimizing technology and its device of sour component at a high temperature of in gasification power generation system - Google Patents

The minimizing technology and its device of sour component at a high temperature of in gasification power generation system Download PDF

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Publication number
CN109983102A
CN109983102A CN201780070958.XA CN201780070958A CN109983102A CN 109983102 A CN109983102 A CN 109983102A CN 201780070958 A CN201780070958 A CN 201780070958A CN 109983102 A CN109983102 A CN 109983102A
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CN
China
Prior art keywords
gas
cyclone separator
additive
gasification
temperature
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CN201780070958.XA
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Chinese (zh)
Inventor
杉村枝里子
滨利雄
泽田圭祐
筱冈卓也
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日立造船株式会社
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Priority to JP2016-224971 priority Critical
Priority to JP2016224971A priority patent/JP6681316B2/en
Application filed by 日立造船株式会社 filed Critical 日立造船株式会社
Priority to PCT/JP2017/032202 priority patent/WO2018092391A1/en
Publication of CN109983102A publication Critical patent/CN109983102A/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023Reducing the tar content
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/024Dust removal by filtration
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/026Dust removal by centrifugal forces
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/08Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/26Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/28Controlling the gas flow through the purifiers

Abstract

A kind of technical problem: the minimizing technology of sour component at a high temperature of providing in gasification power generation system, it can realize higher desalination/desulfurization performance in high-temperature area, and not will lead to tar ingredients be attached to dust, coal tar and rise because the blocking of device causes stress loss.Solution: after gasification process and before cyclone separator treatment process, the gas exported from power generation process is used as additive after recuperation of heat and delivers gas, there is desalination/desulfurizing function cyclone separator upstream side additive to gasifying gas supply, make in the case where gas temperature region is 450~700 DEG C of temperature region in CO2CO used in absorption/modified process2Absorbent carries out CO2It absorbs, works as CO2When uptake reaches saturation, the oxygen of Modified catalytic oxidant layer heating or air are flowed into CO2The positive upstream of absorbent filled layer switches, which is warming up to 800~950 DEG C of temperature region, and makes CO2It is detached from from the absorbent.

Description

The minimizing technology and its device of sour component at a high temperature of in gasification power generation system
Technical field
The imflammable gas for gasifying/being modified and obtain is being carried out by combustion gas wheel using to waste the present invention relates to a kind of In the system that machine, gas engine generate electricity, the sour component in the gasifying gas of removal high temperature is realized with higher removal rate Method and apparatus for carrying out this method.
Background technique
In recent years, it is strongly required the measure of reply global warming, even if in the power generation carried out using waste, also Research improves generating efficiency by getting higher the steam temperature of waste incineration and generating electricity (BTG power generation) and using to waste Imflammable gas and the system to generate electricity by gas turbine, gas engine made of gasifying/being modified are carried out.
In such electricity generation system, the gasification comprising noncombustibles, the various metal classes especially waste of metallic aluminium Generally at 700 DEG C or less, usually in 500~650 DEG C or so lower progress.In modified furnace, the unburned coal of the gas of gasification Burnt, tar ingredients are modified to imflammable gas by vapor.About modified-reaction, in the case where no catalyst, 1000~1200 DEG C or so lower progress, using catalyst, in 800~1000 DEG C or so lower progress.
For example, a kind of gasification power generation system is recorded in patent document 1, by gasification furnace, high temperature dust-collecting equipment, tar Resolving device, purifier apparatus etc. are constituted.In the gasification power generation system, 800~900 DEG C of gas quilt being generated in gasification furnace After having the high temperature dust-collecting equipment dedusting of ceramic filter etc., set to the tar destruction for the decomposition catalyst for having tar ingredients etc. Standby conveying.
It also include H other than unburned coal tar, tar in the gas made of being gasified to waste2、 CH4, the imflammable gas, CO such as CO2, dust, the halogen for being contained in waste, HCl, SO from S2、SO3Gas etc..
In the case where being modified reaction using catalyst, using the modified catalyst of nickel class, precious metal, and due to HCl, the SO being contained in the gas of gasification2、SO3Gas etc. and poison modified catalyst.Such Modified catalytic in order to prevent Agent poisons, and needs to remove poisonous gas ingredient in the upstream of modified furnace.But as documented by the patent document 1 It is only dusted in high temperature dust-collecting equipment without desalination/desulfurization, therefore the performance of the decomposition catalyst of tar ingredients etc. has It may be decreased.
In the past, as the desalination of the refuse burning system for applying dry method etc./desulfurization technology, and known there is following skill Art, that is, calcium hydroxide (Ca (OH) is blown into exhaust stream2), sodium bicarbonate (NaHCO3) etc. powder medicines, and use bag filter Remove the reaction product of solid-like.The technology is applied to 150~200 DEG C of delivery temperature region, the lower removal efficiency of temperature Better.In addition, disclosing a kind of technology (patent document 2) of the purifying thermal decomposition gas of technology as application.In patent document 2 Disclosed in one of technology thermally decomposed by the bag filter of dust removal and the second bag filter of desalination The purifying of gas.Have been removed dust thermal decomposition gas the second bag filter nearby with calcium hydroxide, calcium oxide (CaO), calcium carbonate, sodium bicarbonate, sodium carbonate (Na2CO3) etc. alkaline agents mixing, and make HCl in the second bag filter as solid The reaction product of body is removed, and is applied at 300~600 DEG C close to thermal decomposition temperature region.But in the humidity province Under domain, HCl and carbon dioxide are competed, and to be obtained higher HCl removal rate and just be needed more medicament.In addition, due in dust Without desalination/desulfurization in the bag filter of removal, therefore the purifying for thermally decomposing gas may be insufficient.
In addition, disclosing after a kind of mixture to sodium carbonate and alumina sol dried, pass through crushing/burning At and manufacture sodium aluminate (NaA1O2) class halide absorbent (patent document 3).The partial size of the halide absorbent is 250 ~500 μm, in patent document 3, commenting for halide removal capacity is carried out at 400 DEG C using fixed bed flow type reaction unit Valence.But if fixed bed flow type reaction unit is set to the thermal decomposition gas of waste in the temperature region less than 500 DEG C Body flue and carry out dry type desalination/desulfurization, then since tar ingredients are attached to dust, coal tar, and it is fixedly attached to fixed bed Halogenation absorbent in flow type reaction unit causes stress loss because of blocking and rises, to can not steadily operate.Report Have: for example in the filtration test for having used polystyrene as oil component (tar ingredients), polystyrene is attached to filtering Device;Be attached to the polystyrene of filter if 500 DEG C or more at a temperature of heated if oil component be removed and The pressure loss is set to be restored to original (non-patent literature 1).
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 2006-037012 bulletin
Patent document 2: Japanese Patent Publication 2002-130628 bulletin
Patent document 3: No. 3571219 bulletins of Japanese Patent No.
Non-patent literature
Non-patent literature 1: the evident first-class of coulee thermally decomposes catching for the hydrocarbon ingredient of gas using the polystyrene of ceramic filter Collection/reproducing characteristic, powder engineering meeting magazine, Vo1.40No.11, p19-25,2003
Summary of the invention
(1) technical problems to be solved
It is an object of the present invention in order to solve above-mentioned problem of the prior art, and a kind of gasification power generation system is provided In at a high temperature of sour component minimizing technology and its device, can realize higher desalination/desulfurization performance in high-temperature area, separately Outside, not will lead to tar ingredients be attached to dust, coal tar and because the blocking of device cause stress loss rise.
(2) technical solution
The present invention is to complete to achieve the goals above, and it includes following manners.
(1) in a kind of gasifying electricity generation method at a high temperature of sour component minimizing technology, gasification power generation system includes: to gasification Material carries out the gasification process of part combustion gasification, carries out corase meal trapping place to the gasifying gas exported from the gasification process The cyclone separator treatment process of reason, the gasification for having had been removed corase meal to being exported from the cyclone separator treatment process Gas is dusted the bag filter treatment process of processing, the dedusting to exporting from the bag filter treatment process Gasifying gas carry out CO2Absorption/modification CO2Absorption/modified process and using from the CO2Absorption/modification work The power generation process that the modified gas of sequence output generates electricity, which is characterized in that
It, will be from the gas of the power generation process output after the gasification process and before the cyclone separator treatment process Body is used as additive after recuperation of heat and delivers gas, has on desalination/desulfurizing function cyclone separator to gasifying gas supply Swim side additive;And
Make in the case where gas temperature region is 450~700 DEG C, preferably 540~640 DEG C of temperature region in the CO2It inhales CO used in receipts/modified process2Absorbent carries out CO2It absorbs, works as CO2When uptake reaches saturation, by Modified catalytic oxidant layer liter Warm oxygen or air flows to CO2The positive upstream of absorbent filled layer switches, and the absorbent filled layer is warming up to 800~ 950 DEG C, preferably 850~900 DEG C of temperature region, and make CO2It is detached from from the absorbent.
(2) in gasifying electricity generation method described according to (1) at a high temperature of sour component minimizing technology, feature exists In cyclone separator upstream side additive also has CO2Absorption/removal function.
(3) in gasifying electricity generation method described in (1) or (2) according at a high temperature of sour component minimizing technology, it is special Sign is that the average grain diameter of cyclone separator upstream side additive is 100~1000 μm.
(4) in gasifying electricity generation method described in any one of according to (1)~(3) at a high temperature of sour component removal side Method, which is characterized in that cyclone separator upstream side additive is from dolime, calcium hydroxide, sodium aluminate and bicarbonate It is selected in the group that sodium is constituted.
(5) in the gasifying electricity generation method according to any one of (1)~(4) at a high temperature of sour component minimizing technology, It is characterized in that, after the cyclone separator treatment process and before the bag filter treatment process, it will be from the hair The gas of electrician's sequence output is used as additive after recuperation of heat and delivers gas, supplies to the gasifying gas for having had been removed corase meal Additive, the additive be with desalination/desulfurizing function, and both can be identical with cyclone separator upstream side additive The cyclone separator downstream side additive that can also be different, and from dolime, calcium hydroxide, sodium aluminate and sodium bicarbonate structure At group in select.
(6) in the gasifying electricity generation method according to any one of (1)~(5) at a high temperature of sour component minimizing technology, It is characterized in that, trapping includes the corase meal of the additive in the cyclone separator treatment process, and the trapping is thick Powder supplies together with the gasification materials to the gasification process.
(7) in the gasifying electricity generation method according to any one of (1)~(6) at a high temperature of sour component minimizing technology, It is characterized in that, in the CO2CO used in absorption/modified process2Absorbent is from CaO, Ca (OH)2And dolime It is selected in the group of composition.
(8) in the gasifying electricity generation method according to any one of (1)~(7) at a high temperature of sour component minimizing technology, It is characterized in that, by CO is carried out by NaOH aqueous solution after modified gas recuperation of heat processing2Absorption processing, and recycle/go Except generated Na2CO3
(9) in a kind of gasification power generation system at a high temperature of sour component removal device, the gasification power generation system includes: pair Gasification materials carry out the gasification furnace of part combustion gasification, are set to the downstream of the gasification furnace and to the gasification gas exported from the furnace Body carries out the cyclone separator of corase meal trapping processing, is set to the downstream of the cyclone separator and exports to from this The gasifying gas for being eliminated corase meal is dusted the bag filter of processing, is set to the downstream of the bag filter simultaneously CO is carried out to the gasifying gas of the dedusting exported from this2Absorption/modification CO2Absorption/modification furnace and setting In the CO2Absorption/modification furnace downstream and the generating equipment to be generated electricity using the modified gas exported from the furnace, feature It is,
There is desalination/desulfurization function for supplying being provided with from the flow path that the gasification furnace leads to the cyclone separator The cyclone separator upstream side additive supply line of the additive of energy, and be connected in the supply line from the generating equipment Gas line is delivered, in the CO2Absorption/modification furnace CO2The positive upstream of absorbent filled layer connects aerobic or air supply line, Work as CO2When uptake reaches saturation, the oxygen or air supply line are by the oxygen of modified furnace heating or air to CO2Absorbent is filled out Fill layer switching.
(10) in the gasification power generation system according to (9) at a high temperature of sour component removal device, which is characterized in that Being provided with from the flow path that the cyclone separator leads to the bag filter for supplying there is desalination/desulfurizing function to add Add the cyclone separator downstream side additive supply line of agent, and is connected with the delivery gas from the generating equipment in the supply line Body line.
The average grain diameter of particle is the value using the measurement of laser diffraction formula particle size distribution device.
Present specification and claims throughout in, the gas that part combustion gasification will be carried out to gasification materials and obtained Body is known as " gasifying gas ".
(3) beneficial effect
According to the present invention, by the way that there is desalination/desulfurizing function to gasifying gas supply before cyclone separator treatment process Cyclone separator upstream side additive there is desalination/de- to gasifying gas supply and before bag filter treatment process The cyclone separator downstream side additive of sulfur functional, so as to the gasifying gas to high-temperature region as 450~700 DEG C It realizes higher desalination/desulfurization performance, the catalyst poisoning of modified catalyst can be prevented.
In addition, by using additive as described above so as to prevent tar ingredients be attached to dust, coal tar and because The blocking of device causes stress the problem of loss rises.
Moreover, making in CO2CO used in absorption/modified process2Absorbent 450~700 DEG C gas temperature region into Row CO2It absorbs, works as CO2When uptake reaches saturation, the oxygen of Modified catalytic oxidant layer heating or air are flowed into CO2Absorbent The positive upstream of filled layer switches, which is warming up to 800~900 DEG C of temperature region, and makes CO2From the absorption Agent is detached from, so as to effectively and for good and all remove the CO in gasifying gas2
Detailed description of the invention
Fig. 1 is the flow chart for indicating the gasification power generation system of the embodiment of the present invention.
Fig. 2 is the chart and table for indicating desalination/desulfurizing agent Yu desalination/desulfurization performance relationship.
Fig. 3-1 is the chart (temperature: 550 DEG C) for indicating various desalination/desulfurizing agents Yu desalination/desulfurization performance relationship.
Fig. 3-2 is the chart (temperature: 600 DEG C) for indicating various desalination/desulfurizing agents Yu desalination/desulfurization performance relationship.
Fig. 3-3 is the chart (temperature: 650 DEG C) for indicating various desalination/desulfurizing agents Yu desalination/desulfurization performance relationship.
Specific embodiment
The embodiment of the present invention is shown based on attached drawing.But do not limit the present invention.
Firstly, being illustrated according to Fig. 1 to gasification power generation system.
Gasification power generation system includes: to carry out the gasification furnace 1 of part combustion gasification to gasification materials, be set to gasification furnace 1 Downstream and the bag filter 3 that the gasifying gas exported from the furnace is dusted, the downstream for being set to bag filter 3 and right The gas of dedusting is modified the CO of processing2Absorption/modification furnace 4 and it is set to CO2Absorption/modification furnace 4 downstream is simultaneously The generating equipment 5 to be generated electricity using the modified gas exported from the furnace.
It is being provided with cyclone separator 2 from the flow path that gasification furnace 1 leads to bag filter 3, in the upper of cyclone separator 2 Trip effluent road is connected with cyclone separator upstream side additive supply line 6, the cyclone separator upstream side additive supply line 6 It supplies with desalination/desulfurizing function and preferably also has from additive container 8 and take off CO2The additive of function.In addition, from rotation Wind separator 2 lead to bag filter 3 flow path on be provided with cyclone separator downstream side additive supply line 7, the whirlwind Separator downstream side additive supply line 7, which supplies with desalination/desulfurizing function and preferably also has from additive container 10, to be taken off CO2The additive of function.
Each of additive supply line 6 and cyclone separator downstream side additive supply line 7 in cyclone separator upstream side Top portion is connected with delivery gas via low temperature boiler 13, dehumidifier 14, booster 15 and tank 16 from generating equipment 5 Line 9.
In the CO2Absorption/modification furnace 4 CO2The positive upstream of absorbent filled layer connects aerobic or air supply line 19, The oxygen or air supply line 19 are in CO2The oxygen of modified furnace heating or air are flowed into CO when uptake reaches saturation2It absorbs The switching of agent filled layer.The line 19 is usually to CO2The oxygen of the positive upstream supply heating of absorption/modification furnace 4 catalyst filled layer Or air.
Then, the height in gasifying electricity generation method of the invention is specifically described for each process according to the flow chart of Fig. 1 The minimizing technology of the lower sour component of temperature.
Gasification process
The gasification materials such as waste, RDF, wood chip are subjected to part combustion gasification in gasification furnace 1.From furnace bottom to gasification furnace 1 for oxygen supply and vapor.
Cyclone separator treatment process
It is conveyed from the gasifying gas that the furnace roof of gas stove 1 exports to cyclone separator 2, the particle in gasifying gas is divided into flat The micropowder of corase meal and average grain diameter less than 100 μm that equal partial size is 100 μm or more.Into the gas of cyclone separator 2 Temperature is 700 DEG C hereinafter, preferably 550~650 DEG C, and the temperature of the gas exported from cyclone separator 2 is 550~650 DEG C.
Be blown into from cyclone separator upstream side additive supply line 6 to the upstream-side channel of cyclone separator 2 with desalination/ The additive of desulfurizing function.The additive also has CO preferably except desalination/desulfurizing function2Absorption/removal function.It can It is converted into chloride, sulfate at 700 DEG C or less, is preferably constituted from dolime, calcium hydroxide, sodium aluminate and sodium bicarbonate Group in select.The average grain diameter of the additive is preferably 100~1000 μm, more preferably 300~600 μm.From Cheng Benfang Face considers preferably dolime, and sodium aluminate is preferably from the aspect of desalination/desulfurization degree.In the present embodiment, from addition Agent container 8 has the dolime of several hundred μm of average grain diameter by line 6 to the supply of cyclone separator upstream.
By being blown into the upstream-side channel of cyclone separator 2 with desalination/desulfurizing function, preferably also there is CO2Absorb/ The additive of function is removed, to carry out desalination/desulfurization process to gasifying gas, is preferably able to carry out decarburization acid processing, and It is able to carry out the self purification of the dust, tar that are attached in cyclone separator 2, is able to suppress the pressure of the bag filter in downstream Power loss, and without obstacle carry out its operating.Recycling average grain diameter in bottom by the cyclone separator is 100 ~1000 μm of some or all of corase meal additive, dust, tar, and by the regenerant and the gasification materials one It rises to the gasification furnace 1 and supplies.The modification of the tar in furnace 4 is absorbed/is modified thereby, it is possible to supply the CO in downstream.
Bag filter treatment process
Then, the gasifying gas for having had been removed corase meal exported from cyclone separator 6 is removed to the gas The bag filter 3 of dirt processing conveys.The gasifying gas for having had been removed corase meal includes grain of the average grain diameter less than 100 μm Son.
Using cyclone separator downstream side additive supply line 7 to the flow path from cyclone separator 2 towards bag filter 3 It is blown into desalination/desulfurizing function additive.The additive also has CO preferably except desalination/desulfurizing function2It absorbs/goes Except function.The additive can be converted into chloride, sulfate at 700 DEG C or less, preferably from dolime, calcium hydroxide, aluminium It is selected in the group that sour sodium and sodium bicarbonate are constituted.The average grain diameter of the additive is preferably 20 μm hereinafter, more preferably 15 μ M or less.It is preferably dolime from the aspect of cost, sodium aluminate is preferably from the aspect of desalination/desulfurization degree.Whirlwind point From device downstream side additive and cyclone separator upstream side additive either identical type, is also possible to variety classes.? In the present embodiment, supplied from additive tank 10 by cyclone separator downstream side additive supply line 7 to cyclone separator downstream side To the dolime with 20 μm of average grain diameters below.
By being blown into the downstream-side channel of cyclone separator 2 with desalination/desulfurizing function and preferably also with CO2It inhales Receipts/removal function additive preferably can to carry out desalination/desulfurization process to the gasifying gas for having had been removed corase meal Enough carry out decarburization acid processing.Particularly by desalination/desulfurization process, it is able to extend the CO in downstream2It is general in absorption/modification furnace 4 Ni class modified catalyst service life.
In order to improve the effect of desalination, desulfurization, the average grain diameter of the additive is preferably 20 μm or less.It also can be in whirlwind In the additive of separator downstream side and with well known filter aid.
The average grain diameter of particle is the value using the measurement of laser diffraction formula particle size distribution device.
In the present embodiment, the dust comprising tar ingredients adheres to filter cloth in order to prevent, and makes the filter cake of filter cloth surface The fissility of layer is good, and precoating bag filter is used as bag filter 3.Into the gas for precoating bag filter Temperature is 550~650 DEG C, and the temperature of the gas exported from the bag filter drops to 540~640 DEG C of left sides due to heat dissipation etc. It is right.When the pressure loss becomes larger in precoating bag filter, the cake layer for falling filter cloth surface is brushed lightly by pulse/jet mode, Later, cyclone separator downstream side additive is precoated to filter cloth surface in a short time or in the additive and used mistake Filter the mixture of adjuvant.Pressure loss goal-setting when precoating is 0.5~0.6kPa.Brushing lightly for the cake layer of filter cloth surface is fallen It is preferred that being in 1.5~1.8kPa (153.0~183.5mmH in the pressure loss2It is carried out when range O).
About the amount of precoating, about 20 minutes or so the HCl+SO being blown into gas23 equivalents.Benchmark is needed for precoating Total and about 3.5 hours of the time and steady running time wanted recycle as one.It brushes lightly to fall based on pulse/jet and preferably lead to The pressure loss for crossing bag controls to carry out.
CO2Absorption/modified process
Gasifying gas is after 3 dedusting of bag filter to CO2Absorption/modification furnace 4 conveys.In CO2Absorption/modification furnace 4 is upper Portion is filled with CO2Absorbent has modified catalyst under-filled.As CO2Absorbent and use following compound, 450 CO is based under~700 DEG C, preferably 540~640 DEG C of temperature region2Absorb and carry out carbonation, 800~950 DEG C, it is excellent It is selected as under 850~900 DEG C of temperature region, causes decarburization acid i.e. CO2It is detached from.As CO2The example of absorbent, can enumerate CaO, Ca(OH)2, dolime (CaO/MgO) etc., in the present embodiment, as CO2Absorbent and use CaO.
Make CO to by the switching of the flow path of oxygen or air supply line 192From CO2Absorbent disengaging is illustrated.
1) in common CO2When uptake and transport, the temperature region of gasifying gas is 450~700 DEG C, preferably 540~640 DEG C, CO2The temperature of absorbent is also held in the temperature region.As CO2Absorbent and use CaO in the case where, according to CaO+ CO2→CaCO3Reaction and utilize absorbent absorb removal CO2.The CO in gasifying gas is removed in this way2, thus be easy to Right side carries out following transfer reactions.
CO+H2O→CO2+H2
In this state, it is supplied and is risen to the positive upstream of Modified catalytic oxidant layer by the normal flow paths of oxygen or air supply line 19 Warm oxygen or air.
2) in CO2When uptake reaches saturation, the oxygen or sky of the heating of catalyst filled layer will be used for when running well Gas is switched by the flow path of oxygen or air supply line 19 to CO2The positive upstream of absorbent filled layer supplies, and by the absorbent It is warming up to 800~950 DEG C, preferably 850~900 DEG C of temperature region.Under the temperature region, CO2The carbonating of absorbent Object is thermally decomposed and CO2It is detached from from the absorbent.
In CO2In absorption/modification furnace 4, injecting heating caused by oxygen or air is due to tar ingredients, H2、CO、CH4Oxygen Change reaction heat and generates.
Work as CO2The CO of absorbent2When uptake reaches saturation, it is set to the downstream of high-temperature boiler 11 and indicates gasifying gas In CO2The downstream side CO of concentration2The value of analysis meter 18 is begun to ramp up, therefore as described above, to CO2Absorbent filled layer Positive upstream supply heating oxygen or air.When the absorbent is warming up to 800~950 DEG C, preferably 850~900 DEG C of humidity province When domain, CaCO3Start to decompose, generated CO2Downstream flow.At this point, the CO in gasifying gas2Concentration temporarily on It rises, therefore transfer reaction will not be promoted.CO is set to when utilizing2Absorption/modification furnace 4 upstream simultaneously indicates the CO in gasifying gas2 The upstream side CO of concentration2Analysis meter 17 and the downstream side CO2The CO that analysis meter 18 respectively indicates2When concentration is close, use heating The positive upstream for flowing to Modified catalytic oxidant layer of oxygen or air returns, and the temperature of the catalyst filled layer is dropped to 450~700 DEG C, preferably 540~640 DEG C of range.
1) and 2) above-mentioned operating is repeated later.
By utilizing CO2Absorbent filled layer removes CO2, so as to promote following turns in modified catalyst filled layer Move reaction.
When the typical example as tar assumes toluene, then in CO2The key reaction occurred in absorption/modification furnace 4 is such as Under.
i)C7H8+9O2→7CO2+4H2O oxidation reaction
ii)C7H8+7H2O→7CO+11H2Modified-reaction
iii)CO+H2O→CO2+H2Transfer reaction
Iv) in addition to this, in the presence of oxygen excess ground, H can also occur2、CO、CH4Deng oxidation reaction.
Cooling tower processing
From CO2850~900 DEG C of high-temperature gas of absorption/modification furnace 4 bottom output is transported in high-temperature boiler 11 And recuperation of heat processing has been carried out herein, later, cooling tower 12 is transported at being 170~180 DEG C in temperature.NaOH aqueous solution is cold But thus circulation in tower 12 absorbs the CO in gasifying gas2, and recycle/remove generated Na2CO3Salt.Thus, temperature is not discharged Room effect gas.
Generate electricity process
The cryogenic gas that temperature from the output of cooling tower 12 is 55~60 DEG C, which is delivered to, has gas turbine, gas engine Generating equipment 5, and be used herein to generate electricity.
Deliver gas
The temperature being discharged from generating equipment 5 is after 400 DEG C of gas then carries out recuperation of heat processing by low temperature boiler 13 one Part at 170~180 DEG C to atmosphere be discharged, be left part by delivery gas line 9 via dehumidifier 14, booster 15 and Tank 16 and be transported to cyclone separator upstream side additive supply line 6 and cyclone separator downstream side additive supply line 7 Each starting ends, and it is used as the delivery gas (gas of cyclone separator upstream side additive and cyclone separator downstream side additive Temperature is 50 DEG C).Oxygen concentration in the gas is 1~2 capacity % or so, exit gas of the delivery gas to gasification furnace Injection ratio is 1/15~1/30, thus will not due to fuel gas burning and cause low heat valve (LHV) reduce.
Experimental example
Experimental example of the invention is then shown.
Using waste gasify/be modified and the system shown in FIG. 1 that generates electricity of the imflammable gas that obtains In, change each condition and is tested.An example of the composition of the exit gas of gasification furnace 1 is shown in table 1, is shown in table 2 Gasification furnace 1 and CO2Desalination/de- is shown in FIG. 2 in absorption/modification furnace 4 temperature and air ratio relative to each exit gas Sulphur agent and desalination/desulfurization performance relationship, are shown in table 3 the air ratio relative to exit gas of generating equipment 5, in table 4 And desalination/desulfurizing agent everywhere and desalination/desulfurization performance relationship are shown in Fig. 3, it is shown in table 5 the life about calcium carbonate At/decompose Calculation of thermodynamic equilibrium result.
According to table 5, in CO2In absorption tower, entrance CO2It is 8.1%, passes through the CO of EQUILIBRIUM CALCULATION FOR PROCESS 96.98% at 600 DEG C2 It is absorbed removal (being 89.37% at 650 DEG C).In addition, decomposing outlet when the temperature on absorption tower is warming up to 850 DEG C CO2Concentration is 38.59% (decomposing 79.48% at 900 DEG C).
[table 1]
[table 2]
[table 3]
GE exit gas vsGE air ratio
[table 4]
[table 5]

Claims (10)

1. the minimizing technology of sour component, gasification power generation system include: at a high temperature of in a kind of gasifying electricity generation method
The gasification process of part combustion gasification is carried out to gasification materials, the gasifying gas exported from the gasification process is carried out slightly The cyclone separator treatment process of powder trapping processing has had been removed slightly to what is exported from the cyclone separator treatment process The gasifying gas of powder is dusted the bag filter treatment process of processing, exports to from the bag filter treatment process Dedusting gasifying gas carry out CO2Absorption/modification CO2Absorption/modified process and using from the CO2It inhales The power generation process that receipts/modified process output modified gas generates electricity, which is characterized in that
After the gasification process and before the cyclone separator treatment process, will from the power generation process gas that exports It is used as additive after recuperation of heat and delivers gas, there is desalination/desulfurizing function cyclone separator upstream to gasifying gas supply Side additive;And
Make in the case where gas temperature region is 450~700 DEG C of temperature region in the CO2CO used in absorption/modified process2 Absorbent carries out CO2It absorbs, works as CO2When uptake reaches saturation, by the flow direction of the oxygen of Modified catalytic oxidant layer heating or air CO2The positive upstream of absorbent filled layer switches, and the absorbent filled layer is warming up to 800~950 DEG C of temperature region, and makes CO2It is detached from from the absorbent.
2. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method according to claim 1, which is characterized in that
Cyclone separator upstream side additive also has CO2Absorption/removal function.
3. the minimizing technology of sour component, feature exist at a high temperature of in gasifying electricity generation method according to claim 1 or 2 In,
The average grain diameter of cyclone separator upstream side additive is 100~1000 μm.
4. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method described in any one of claim 1 to 3, It is characterized in that,
The group that cyclone separator upstream side additive is constituted from dolime, calcium hydroxide, sodium aluminate and sodium bicarbonate Middle selection.
5. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method according to any one of claims 1 to 4, It is characterized in that,
It, will be defeated from the power generation process after the cyclone separator treatment process and before the bag filter treatment process Gas out is used as additive after recuperation of heat and delivers gas, supplies additive to the gasifying gas for having had been removed corase meal, The additive be with desalination/desulfurizing function, and with cyclone separator upstream side additive both can it is identical can also be with Different cyclone separator downstream side additives, and the group constituted from dolime, calcium hydroxide, sodium aluminate and sodium bicarbonate Middle selection.
6. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method according to any one of claims 1 to 5, It is characterized in that,
Trapping includes the corase meal of the additive in the cyclone separator treatment process, and by the trapping corase meal and institute Gasification materials are stated to supply to the gasification process together.
7. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method described according to claim 1~any one of 6, It is characterized in that,
In the CO2CO used in absorption/modified process2Absorbent is from CaO, Ca (OH)2And the group that dolime is constituted Middle selection.
8. the minimizing technology of sour component at a high temperature of in gasifying electricity generation method according to any one of claims 1 to 7, It is characterized in that,
CO will be carried out by NaOH aqueous solution after modified gas recuperation of heat processing2Absorption processing, and recycle/remove and is produced Na2CO3
9. the removal device of sour component at a high temperature of in a kind of gasification power generation system, the gasification power generation system include:
The gasification furnace of part combustion gasification is carried out to gasification materials, is set to the downstream of the gasification furnace and to exporting from the furnace Gasifying gas carries out the cyclone separator of corase meal trapping processing, is set to the downstream of the cyclone separator and to defeated from this The gasifying gas for having had been removed corase meal out is dusted the bag filter of processing, is set to the bag filter Downstream simultaneously carries out CO to the gasifying gas of the dedusting exported from this2Absorption/modification CO2Absorption/modification furnace, with And it is set to the CO2Absorption/modification furnace downstream and the generating equipment to be generated electricity using the modified gas exported from the furnace, It is characterized in that,
There is desalination/desulfurizing function for supplying being provided with from the flow path that the gasification furnace leads to the cyclone separator The cyclone separator upstream side additive supply line of additive, and the delivery from the generating equipment is connected in the supply line Gas line, in the CO2Absorption/modification furnace CO2The positive upstream of absorbent filled layer connects aerobic or air supply line, works as CO2 When uptake reaches saturation, the oxygen or air supply line are by the oxygen of modified furnace heating or air to CO2Absorbent filled layer Switching.
10. the removal device of sour component at a high temperature of in gasification power generation system according to claim 9, which is characterized in that
There is desalination/desulfurization function for supplying being provided with from the flow path that the cyclone separator leads to the bag filter The cyclone separator downstream side additive supply line of the additive of energy, and be connected in the supply line from the generating equipment Deliver gas line.
CN201780070958.XA 2016-11-18 2017-09-07 The minimizing technology and its device of sour component at a high temperature of in gasification power generation system CN109983102A (en)

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