CN1747774A - Method and apparatus for separating and recovering carbon dioxide - Google Patents

Method and apparatus for separating and recovering carbon dioxide Download PDF

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Publication number
CN1747774A
CN1747774A CNA2004800035325A CN200480003532A CN1747774A CN 1747774 A CN1747774 A CN 1747774A CN A2004800035325 A CNA2004800035325 A CN A2004800035325A CN 200480003532 A CN200480003532 A CN 200480003532A CN 1747774 A CN1747774 A CN 1747774A
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carbon dioxide
absorption
gas
regeneration
absorbing
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CN1747774B (en
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河野巧
林干洋
风间伸吾
小野透
河村隆文
高桥耕治
原田修一
中山秀明
臼杵正好
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Nippon Steel Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456Removing acid components
    • B01D53/1475Removing carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/62Carbon oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0233Other waste gases from cement factories
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

Abstract

A method for separating and recovering carbon dioxide from a by-produced gas and the like generated in an ironworks by the chemical absorption method, characterized in that it comprises utilizing the low quality waste heat generated in an ironworks in the process wherein carbon dioxide is absorbed by a chemical absorption fluid from said gas and then the carbon dioxide is separated by heating the chemical absorption fluid.

Description

The separation and recovery method of carbon dioxide and device
Technical field
The present invention relates to separate recovery carbon dioxide (the following CO that only abbreviates as 2) method and device.In more detail, relate to such CO 2Separation and recovery method and device, reclaim CO when using chemical absorption method to separate 2The time, at first come from by a plurality of CO with the absorbing medium absorption 2(generation) source is supplied with contains CO 2CO in the gas 2, will finish CO then 2The absorbing medium that absorbs puts together in a place regenerates, thereby can improve device efficiency, can utilize and CO 2(generation) source is in the heat extraction of different places.
Furtherly, the present invention relates to following CO 2Separation and recovery method, this separation and recovery method utilization or flexible Application have extensive CO 2Even carry out the heat extraction that recuperation of heat also is difficult to low-grade (low temperature) that utilizes, wherein CO as heat extraction in the steel plant in generation source 2Come from secondary angry body (unburned gas), its burning and gas-exhausting or its modifying process process gas etc. and contain CO 2Gas.
Background technology
In recent years, the countermeasure of reply global warming issue is subjected to powerful propelling for the center as follows, for example in the fabrication stage with utilize the energy-conservation propelling in stage, new forms of energy such as solar energy, wind energy, bio-fuel apply flexibly and to the conversion of low environmental load fuel such as natural gas etc.
On the other hand, be intended to separate the greenhouse gases (carbon dioxide) that recovery produces and isolated, immobilized research also advances energetically.For example, the scheme that has proposed to utilize chemical absorption method from the burnt gas in thermal power plant, to separate and reclaim carbon dioxide (for example, with reference to clear former positive height, from generating with reclaiming CO the boiler exhaust 2Test, energy resources, energy resources association, 1993, the 14th volume, the 1st phase, p.91~97).According to this scheme, although different with the difference of condition, the separation rate of recovery of carbon dioxide can reach 90%.
Yet, when separating the recovery carbon dioxide the burning and gas-exhausting that adopts chemical absorption method from such thermal power plant (generating boiler exhaust), the gas concentration lwevel that contains in the burning and gas-exhausting in thermal power plant is low to moderate a few volume %~tens volume %, thereby the employed equipment of chemical absorption method will become very huge.In addition, when adopting chemical absorption method to separate the recovery carbon dioxide, heat energy becomes the reason that plays a decisive role aspect operating cost.
But, this single technology has been carried out optimized thermal power plant in order to generate electricity, heat extraction that can the flexible Application chemical absorption method, for this reason, have to take following method, new heat energy generation equipment perhaps is set, perhaps is used to the steam that generates electricity, this will cause the reduction of generating efficiency.
On the other hand, when the carbon dioxide sequestration that will separate recovery is in ground or in the ocean, do not have advantage (just increasing cost) at economic aspect, even want effectively to be used as chemical raw material etc., in that in Japan market is less, satisfy the demand basically, have the not enough problem of configuration aspects like this of driving force economically.
Summary of the invention
So, the objective of the invention is to: provide a kind of and compare, with small-scale equipment, effectively and at an easy rate separate the technology of recovery from the carbon dioxide of steel plant's discharging in one of extensive carbon dioxide generation source with the situation in thermal power plant.
In addition, another object of the present invention is: provide a kind of carbon dioxide that is in different places by combination the source to take place with the regeneration of absorption solution thermal source, effectively and at an easy rate separate the technology that reclaims carbon dioxide from carbon dioxide generation source.
So, the present inventor is for achieving the above object, concentrate on studies with regard to separating the technology that reclaims the carbon dioxide that discharges from large-scale carbon dioxide generation source, the result distinguishes: it is different with the burning and gas-exhausting that fossil fuel burns in air as large-scale carbon dioxide the secondary angry bodies (unburned gas) such as blast furnace gas that the steel plant in source produce to take place, the ratio of its carbon dioxide (concentration) is higher, reaches more than 20 %~more than 30 %.
Learn from this result: when adopting chemical absorption method to separate the recovery carbon dioxide, compare, be used to separate the equipment miniaturization significantly of reclaiming with the carbon dioxide of amount with the situation in thermal power plant.
In addition, steel plant are made of blast furnace, converter, sintering, coke oven, heating furnace, casting, many technologies such as rolling, carry out various improvement for energy-conservation, can think in iron and steel technology the only remaining low-grade heat energy in leeway that do not use.
But also learn: chemical absorbing liquid be heated into the reason that aspect operating cost, plays a decisive role, if this energy was pined for being used or applying flexibly in adding of chemical absorbing liquid, then can reduce the operating cost of chemical absorption method significantly.
Furtherly, learnt that the angry body of above-mentioned pair can be used as fuel gas and used in iron-smelting process,, can improve the energy density of this gas, can improve the thermal efficiency of subsequent technique by in its way, extracting carbon dioxide.
Furtherly, also learn the burning gases that utilize in steel plant's internal combustion behind the secondary angry bodies such as converter gas, with the CO that contains up to the ratio of more than 30 % 2, can be used in and separate the equipment miniaturization more of reclaiming carbon dioxide.
Based on above opinion, the present inventor has finished the present invention.
Moreover, the present inventor attempts to analyze the separation cost recovery of the carbon dioxide that adopts chemical absorption method, drawn following conclusion: the essential factor of maximum cost is the thermal source of regenerating carbon dioxide absorbing medium, and its high efficiency is effective for realizing effectively and separating recovery carbon dioxide this purpose at an easy rate.
That is to say, can reach the present invention by the separation and recovery method and the device of the described carbon dioxide in following (1)~(22).
(1) a kind of chemical absorption method that adopts separates the method that reclaims carbon dioxide from the secondary angry body that steel plant produce, it is characterized in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, at this chemical absorbing liquid of heating carbon dioxide is able in the separation processes, utilizes or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
(2) a kind of chemical absorption method that adopts separates the method that reclaims carbon dioxide from the burning and gas-exhausting of the secondary angry body of steel plant's generation, it is characterized in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, at this chemical absorbing liquid of heating carbon dioxide is able in the separation processes, utilizes or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
(3) a kind of chemical absorption method that adopts separates the method that reclaims carbon dioxide from the process gas that modifying process produces, wherein modifying process is used for producing hydrogen from the secondary angry body that steel plant produce, described method is characterised in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, make in the technology of carbon dioxide separation at this chemical absorbing liquid of heating, utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
(4) according to the separation and recovery method of each described carbon dioxide of above-mentioned (1)~(3), it is characterized in that: supply with gas concentration lwevel in the angry body of above-mentioned pair, burning and gas-exhausting or the process gas of above-mentioned chemical absorption method and be 15 volume % or more than.
(5) according to the separation and recovery method of each described carbon dioxide of above-mentioned (1)~(4), it is characterized in that: the angry body of above-mentioned pair is at least a kind among blast furnace gas, oven gas and the converter gas.
(6) according to the separation and recovery method of each described carbon dioxide of above-mentioned (1)~(5), it is characterized in that: the heat extraction that all or part of of the necessary heat of regeneration of above-mentioned chemical absorbing liquid uses steel plant to produce.
(7) according to the separation and recovery method of each described carbon dioxide of above-mentioned (1)~(6), it is characterized in that:, apply flexibly the suitable heat extraction that steel plant produce for the regeneration of chemical absorbing liquid is multistage according to the characteristic of above-mentioned chemical absorbing liquid.
(8) according to the separation and recovery method of each described carbon dioxide of above-mentioned (1)~(7), it is characterized in that:, use factory's steam simultaneously for the regeneration of above-mentioned chemical absorbing liquid utilizes or apply flexibly the heat extraction that steel plant produce as far as possible.
(9) a kind of device that reclaims carbon dioxide that separates from carbon dioxide generation source is characterized in that the formation of this device comprises:
Carbon dioxide absorption equipment: be used for adopting carbon dioxide absorption medium absorbing carbon dioxide from the gas of supplying with by carbon dioxide generation source that contains carbon dioxide;
Absorbing medium reclaim equiment: be used for utilizing absorbing medium regeneration to use the thermal source separating carbon dioxide with the regeneration absorbing medium from the absorbing medium that has absorbed carbon dioxide;
The carbon dioxide absorption medium: the pumped (conveying) medium as carbon dioxide circulates at two equipment rooms; And
Send pipe arrangement and return pipe arrangement: be used for the transport of carbon dioxide absorbing medium;
Wherein, the absorption equipment of above-mentioned carbon dioxide is arranged near the carbon dioxide generation source, and above-mentioned absorbing medium reclaim equiment is arranged on and carbon dioxide generation different place, residing place, source.
(10) according to the separating and reclaiming device of above-mentioned (9) described carbon dioxide, it is characterized in that: the relational expression of A<C and B<C is satisfied in the distance A between above-mentioned carbon dioxide generation source and the carbon dioxide absorption equipment, absorbing medium reclaim equiment and absorbing medium regeneration with the distance C apart between B and carbon dioxide absorption equipment and the absorbing medium reclaim equiment between the thermal source.
(11) according to the separating and reclaiming device of above-mentioned (9) or (10) described carbon dioxide, it is characterized in that: be used for the source taking place and supply with sending the pipe arrangement distance Y and returning pipe arrangement apart from Z and be used for from absorbing medium regeneration with thermal source of the pipe arrangement distance X of the gas that contains carbon dioxide, above-mentioned carbon dioxide absorption medium at least one relational expression that satisfies between the pipe arrangement distance W of absorbing medium reclaim equiment heat supply among 2X<relational expression (Y+Z) and the relational expression (X+W)<(Y+Z) to carbon dioxide absorption equipment from above-mentioned carbon dioxide.
(12) according to the separating and reclaiming device of each described carbon dioxide of above-mentioned (9)~(11), it is characterized in that: above-mentioned absorbing medium reclaim equiment is arranged on and is used as absorbing medium regeneration with near the technical process heat extraction source of thermal source.
(13) according to the separating and reclaiming device of each described carbon dioxide of above-mentioned (9)~(12), it is characterized in that: utilize the technical process heat extraction as above-mentioned regeneration of absorption solution part or all with thermal source.
(14) according to the separating and reclaiming device of each described carbon dioxide of above-mentioned (9)~(13), it is characterized in that: the formation of this separating and reclaiming device comprises above-mentioned 1 cover or overlaps carbon dioxide absorption equipment and 1 cover or overlap regeneration of absorption solution equipment more more.
(15) according to the separating and reclaiming device of each described carbon dioxide of above-mentioned (9)~(14), it is characterized in that: as above-mentioned regeneration of absorption solution part or all, the multistage technical process heat extraction that utilizes the different temperatures level with thermal source.
(16) a kind of method that reclaims carbon dioxide of separating from carbon dioxide generation source, it is characterized in that: adopt the carbon dioxide absorption equipment that is provided with near carbon dioxide generation source, utilize carbon dioxide absorption medium absorbing carbon dioxide from the gas of supplying with by this carbon dioxide generation source that contains carbon dioxide, utilize regeneration of absorption solution to heat this carbon dioxide absorption medium with thermal source afterwards, employing makes carbon dioxide separation with the regeneration of absorption solution equipment that carbon dioxide generation source is in different places.
(17) according to the separation and recovery method of above-mentioned (16) described carbon dioxide, it is characterized in that: the distance C apart between B and carbon dioxide absorption equipment and the absorbing medium reclaim equiment between the thermal source of the distance A between above-mentioned carbon dioxide generation source and the carbon dioxide absorption equipment, absorbing medium reclaim equiment and absorbing medium regeneration usefulness satisfies the relational expression of A<C and B<C.
(18) according to the separation and recovery method of above-mentioned (16) or (17) described carbon dioxide, it is characterized in that: be used for the source taking place and supply with sending the pipe arrangement distance Y and returning pipe arrangement apart from Z and be used for from absorbing medium regeneration with thermal source of the pipe arrangement distance X of the gas that contains carbon dioxide, above-mentioned carbon dioxide absorption medium at least one relational expression that satisfies between the pipe arrangement distance W of absorbing medium reclaim equiment heat supply among 2X<relational expression (Y+Z) and the relational expression (X+W)<(Y+Z) to carbon dioxide absorption equipment from above-mentioned carbon dioxide.
(19) according to the separation and recovery method of each described carbon dioxide of above-mentioned (16)~(18), it is characterized in that: above-mentioned absorbing medium reclaim equiment is arranged on and is used as absorbing medium regeneration with near the technical process heat extraction source of thermal source.
(20) according to the separation and recovery method of each described carbon dioxide of above-mentioned (16)~(19), it is characterized in that: utilize the technical process heat extraction as above-mentioned regeneration of absorption solution part or all with thermal source.
(21) according to the separation and recovery method of each described carbon dioxide of above-mentioned (16)~(20), it is characterized in that: this separation and recovery method uses above-mentioned 1 cover or overlaps carbon dioxide absorption equipment and 1 cover or overlap regeneration of absorption solution equipment more more.
(22) according to the separation and recovery method of each described carbon dioxide of above-mentioned (16)~(21), it is characterized in that: as above-mentioned regeneration of absorption solution part or all, the multistage technical process heat extraction that utilizes the different temperatures level with thermal source.
Description of drawings
Fig. 1 is used for adopting chemical absorption method to separate the process principle figure that reclaims carbon dioxide from the unstrpped gas that contains carbon dioxide.
Fig. 2 is that expression is used for adopting chemical absorption method to separate the schematic diagram of the technology that reclaims carbon dioxide from the unstrpped gas that steel plant produce, whole as the necessary heat of regeneration of chemical absorbing liquid wherein, utilization be the heat extraction of steel plant's generation.
Fig. 3 is that expression is used for adopting chemical absorption method to separate the schematic diagram of the technology that reclaims carbon dioxide from the unstrpped gas that steel plant produce, wherein according to the characteristic of chemical absorbing liquid, multistagely for the regeneration of chemical absorbing liquid apply flexibly the suitable heat extraction that steel plant produce.
Fig. 4 is that expression is used for adopting chemical absorption method to separate the schematic diagram of the technology that reclaims carbon dioxide from the unstrpped gas that steel plant produce, and wherein applies flexibly the heat extraction that steel plant produce for the regeneration of chemical absorbing liquid, also applies flexibly factory's steam simultaneously.
Fig. 5 is the representative schematic representation of apparatus of expression the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Fig. 6 is other representative schematic representation of apparatus of expression the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Fig. 7 is the 3rd a representative schematic representation of apparatus of expression the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Fig. 8 is the 4th a representative schematic representation of apparatus of expression the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Fig. 9 is the 5th a representative schematic representation of apparatus of expression the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Figure 10 is the schematic representation of apparatus that expression is used for the concrete example 1 of the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Figure 11 is the schematic representation of apparatus that expression is used for the concrete example 2 of the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Figure 12 is the schematic representation of apparatus that expression is used for the concrete example 3 of the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Figure 13 is the schematic representation of apparatus that expression is used for the concrete example 4 of the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
Figure 14 is the schematic representation of apparatus that expression is used for the concrete example 5 of the 2nd embodiment of the present invention, is that expression is used for by the carbon dioxide of combination different places the device (technology) that reclaims carbon dioxide is separated in the source with the regeneration of absorption solution thermal source figure taking place.
The specific embodiment
Enumerating specific embodiment (perhaps embodiment) below describes together with each important document with regard to the present invention.Much less, the present invention ought to not can be limited to these embodiments.
The 1st embodiment of the present invention is to adopt chemical absorption method to separate the method that reclaims carbon dioxide from the unstrpped gas that steel plant produce, it is characterized in that: as unstrpped gas, what use is to be selected from the secondary angry body that steel plant produce, the burning and gas-exhausting of the angry body of this pair, and at least a kind of gas among the process gas that in modifying process, produces, wherein said modifying process is used for producing hydrogen from the angry body of this pair, with chemical absorbing liquid from this unstrpped gas behind the absorbing carbon dioxide, make in the technology of carbon dioxide separation at this chemical absorbing liquid of heating, utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
(factory that the separation and recovery method of the present embodiment may be suitable for)
The factory that the separation and recovery method of the present embodiment may be suitable for, for example so long as the steel plant that can from blast furnace, converter, coke oven etc., produce secondary angry body and may supply with 500 ℃ or following low-grade heat extraction just, not what special restriction.
(unstrpped gas)
The employed unstrpped gas of the separation and recovery method of the present embodiment can be the secondary angry body (unburned gas) that steel plant produce.Though also difference along with the difference of steel plant's structure, but with blast furnace associating steel plant (integrated steelmaking plant) is example, as unstrpped gas, can list blast furnace gas (BFG), oven gas (COG) and converter gas (LDG), in addition, also comprise the gas (process gas) that to produce hydrogen be purpose, produce in the process (technology) of secondary angry bodies such as upgrading COG and LDG.
These secondary angry bodies can use a kind separately, also two or more mixing can be used with admixture.In addition, the separation and recovery method of the present embodiment is a unstrpped gas with the burning and gas-exhausting of the angry body of above-mentioned pair, also can supply with the separation of carbon dioxide and reclaim.
When these unstrpped gases (steel plant produce secondary angry body or its burning and gas-exhausting) can be used as high-grade heat extraction when being used, then in the present invention, these gases are used after finishing as the utilization of high-grade heat extraction again, because the temperature when adopting the chemical absorption method absorbing carbon dioxide can be near the temperature the normal temperature.
These unstrpped gases can reclaim a kind of separation of supplying with carbon dioxide wherein individually, also two or more can be mixed the separation of supplying with carbon dioxide and reclaim.In the mixed style of two or more, except that the burning and gas-exhausting mixed style each other of each other mixed style of secondary angry body, secondary angry body, also comprise the burning and gas-exhausting of secondary angry body and the mixed style of secondary angry body.
In these unstrpped gases, the ratio of the carbon dioxide of BFG is up to more than 20 %, and as other propellant composition, hydrogen content is several %, and carbon monoxide content is more than 20 %.COG is rich in hydrogen and the methane that is suitable for use as fuel gas, and in the exhaust after the burning (also claiming burning and gas-exhausting), concentration of carbon dioxide reaches more than 20 %.
On the other hand, LDG contains the carbon dioxide of more than 10 %, contains the carbon monoxide about 70% simultaneously, and in the waste gas after burning (burning and gas-exhausting), gas concentration lwevel is very high, reaches more than 30 %.
Therefore, as unstrpped gas, preferably use the burning and gas-exhausting of the carbon dioxide ratio BFG higher, BFG, the burning and gas-exhausting of COG, the burning and gas-exhausting of LDG and the mist of these gas and other gas than the carbon dioxide in thermal power plant.
In addition, the gas that produces in the process of producing hydrogen at upgrading COG and LDG as described later also is suitable.
Specifically, the ratio (concentration) of the carbon dioxide from the unstrpped gas that these steel plant produce be 15 volume % or more than, be preferably 18 volume % or more than, more preferably 20 volume % or more than, more preferably 22 volume % or more than, be preferably especially 25 volume % or more than.
When from the higher gas of these carbon dioxide ratios, separate reclaiming carbon dioxide with means such as chemical absorption methods, (thermal power plant of natural gas is about 8% with burning and gas-exhausting that the gas concentration lwevel in thermal power plant is lower, coal fire power power plant is about 12%) compare as the situation of unstrpped gas, the scale that can reduce equipment significantly (for example, with from the lower burning and gas-exhausting of the gas concentration lwevel in coal fire power power plant, separate the situation that reclaims carbon dioxide and compare, under the situation of BFG as raw material coal gas of using steel plant, cost of equipment may be cut down about 3 one-tenth).
(process for separating and recovering of carbon dioxide)
In the separation and recovery method of the present embodiment, adopt chemical absorption method from unstrpped gas, to separate and reclaim carbon dioxide.And,, need to separate yield and reach 1,000,000 tons/year large-scale capacity of equipment when separating from steel plant when reclaiming carbon dioxide as large-scale CO2 emission source as the countermeasure of global warming.In this case, the separation and recovery method of the carbon dioxide maximum and that popularize the most of exploitation at present is a chemical absorption method, and the present invention also selects this chemical absorption method for use.
Use the technological principle of description of drawings chemical absorption method below.Fig. 1 is that expression is used for adopting chemical absorption method to separate the process principle figure that reclaims carbon dioxide from the unstrpped gas that contains carbon dioxide.
As shown in Figure 1, chemical absorption method is chemical absorbing liquid to be circulated and the method that is used between absorption tower 1 and regenerator 7, that is: use the chemical absorbing liquid of amine etc., in the reaction tower that is called as absorption tower 1 as carbon dioxide absorption equipment, the unstrpped gas 3 that contains carbon dioxide is contacted about 50 ℃ with chemical absorbing liquid 5 as the carbon dioxide absorption medium, after chemical absorbing liquid has absorbed carbon dioxide, by pipe arrangement 6 this liquid is delivered in the regenerator 7 as regeneration of absorption solution equipment, employing is heated to about 120 ℃ as the heat medium 9 of regeneration of absorption solution with thermal source, separated from chemical absorbing liquid by regenerator 7 then and reclaim carbon dioxide, the chemical absorbing liquid through regenerating turns back to absorption tower 1 by returning pipe arrangement 8.
In above-mentioned chemical absorbing liquid, what can be suitable for using be the known solution in the past such as the aqueous solution that contains amine etc., is not defined as specific solution especially.
In the separation and recovery method of the present embodiment, above-mentioned regenerator heats necessary heat energy and become the reason that this separation recovery method plays a decisive role aspect operating cost.So, in the separation and recovery method of the present embodiment, as the regeneration of absorption solution thermal source, utilize or apply flexibly steel plant produce 500 ℃ or following, be preferably 400 ℃ or following low-grade heat extraction.
That is to say, the separation and recovery method of the present embodiment is because utilize or apply flexibly low-grade heat energy of being difficult in the iron-smelting process utilize (even in low-grade heat energy, also preferably utilize as far as possible or apply flexibly the heat energy of high temperature), therefore, it can be as the thermal power plant, heat energy is set produces equipment, perhaps use the steam that in generating, uses to produce heating steam (heat medium 9).
Therefore, adopt chemical absorption method can reduce the separation cost recovery of carbon dioxide significantly.In addition, as top narrate since unstrpped gas in concentration of carbon dioxide higher, therefore, not only can make equipment become compact, and the use amount of the needed public utility of equipment (electric power and water) also can be cut down, and can further be reduced operating cost.
At this, the low-grade heat extraction that why will utilize in the technology of separating carbon dioxide or apply flexibly, steel plant produce is set at 500 ℃ or following, is based on following reason:
That is to say, the heat extraction that surpasses 500 ℃ is that present steel plant are used as high-grade heat extraction, under the situation of using this heat extraction, the same with the generating that utilizes (migrating) thermal power plant with the situation of steam, perhaps cause the reduction of production efficiency, perhaps need to be provided with new thermal source generation equipment to replenish the part of migrating, therefore, be difficult to reach and separate the purpose that reclaims carbon dioxide at an easy rate.
But, when utilizing or applying flexibly steel plant produce 500 ℃ or following low-grade heat extraction in the technology at separating carbon dioxide, for example on the degree that does not influence iron-smelting process one side, use a part to surpass 500 ℃ the high-grade heat extraction and the combustion heat of fuel slightly simultaneously, this situation is also included within the technical scope of the present invention.
That is to say that the separation and recovery method of the present embodiment can not be interpreted as to narrow sense certainly: in the technology of separating carbon dioxide, can only utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
Above-mentioned separation and recovery method also can utilize the high-grade heat extraction that surpasses 500 ℃ and the combustion heat of fuel in the scope that does not break away from purpose of the present invention.
500 ℃ or following low-grade heat extraction as steel plant's generation, for example can list the heat extraction (about 350 ℃) that comes from sintering finished cooler, sintering master emission gases (about 280 ℃), hot-blast stove exhaust (about 230 ℃), sintering master emission gases (about 180 ℃), blast furnace water quenching with the low-grade heat energy that is difficult to utilize in the draining iron-smelting process such as (about 90 ℃), but the present invention ought to be not limited to these.
In present steel plant, in order to be hydrogen-rich gas through the water vapour upgrading with angry body COG of pair and LDG, use the highly purified hydrogen of recovery such as water vapour modifying apparatus of oxygen burning and usefulness, be used in the converters of exhaust in iron-smelter after simultaneously hydrogen being reclaimed etc. etc., the form of utilizing of these gases is improved and complicated more.
Therefore, the low-grade heat extraction that produces by the equipment that enrolls steel plant's (steel plant or technology) is also included within the low-grade heat extraction of separation and recovery method of the present embodiment.For example, preferably utilize or apply flexibly the heat extraction temperature that comes from sintering finished cooler or following low-grade heat extraction.Surpass sintering finished cooler heat extraction temperature (about 350 ℃) although heat extraction depend on the formation of steel plant, in the present FA iron-smelter of energy recovery technology, effectively utilize as the high-grade thermal source.
In addition, about the heat extraction temperature, why do not stipulate concrete temperature (numerical value), be because adopt chemical absorption method to separate the variation of the distance of the technology (or equipment) that reclaims carbon dioxide and outside air temperature etc., supply with and adopt chemical absorption method to separate the technology utilization that reclaims carbon dioxide or the temperature when applying flexibly has some change along with the heat extraction that imposes a condition, will come from sintering finished cooler of sintering finished cooler is transported to.
More preferably, utilize as far as possible or apply flexibly the heat extraction of the heating-up temperature (about 120 ℃) that temperature is higher than the chemical absorbing liquid of regenerator to carry out Steam Heating.This is that the desired equipment of heat exchange may be more little, and then can reduce CO because the temperature difference of chemical absorbing liquid and heat extraction is big more 2The separation cost recovery.
In addition, why stipulate the low-grade heat extraction that " utilize or apply flexibly " is such, be because low-grade heat extraction directly can be utilized as the employed heat medium of the heating of regenerator (heat energy) in addition, also can keep using aspect the predetermined temperature heat medium (for example steam etc.) in heating.
Device constitute simple and the few this point of heat loss on, the former (directly utilizing) is preferred; On the chemical absorbing liquid with regenerator maintained easy control this point under the steady temperature, latter's (applying flexibly) was preferred.
When heat medium during, because causing corrosion and impurity in the pipe arrangement, corrosion composition that contains in the low-grade heat extraction (draining or exhaust) and impurity piles up, in order not reduce pyroconductivity, preferred these corrosion compositions and the impurity removed in advance by low-grade heat extraction.
In addition, in the separation and recovery method of the present embodiment, can (as single heat extraction) use or apply flexibly above-mentioned low-grade heat extraction (heat energy) individually, also can use or apply flexibly the low-grade heat extraction of two or more jointly.When and when heat medium being heated to predetermined temperature with two or more heat extraction, also can begin to heat heat medium from the lower heat extraction of temperature in the mode that the heat extraction temperature increases progressively.At this moment, if last heat energy deficiency also can be burnt with fuel.
That is to say, in the separation and recovery method of the present embodiment, may not be only limited in the technology that adopts chemical absorption method separation recovery carbon dioxide and utilize or apply flexibly the situation of low-grade heat extraction, in iron-smelter except the our factory consume, also can be with the part of the fuel gas sold as domestic gas etc. as auxiliary fuel.
The utilization accompanying drawing carries out such embodiment briefly bright below.In addition, Fig. 2~4 shown below and Fig. 1 and then the same symbols of mark such as device same with Fig. 2~3.
Fig. 2 is that expression adopts chemical absorption method to separate the schematic diagram of the technology that reclaims carbon dioxide from the unstrpped gas (Fig. 2 is the example of the angry body of vice) of steel plant's generation, wherein as whole (the perhaps parts) of the necessary heat of regeneration of chemical absorbing liquid, utilization be the heat extraction that steel plant produce.
In embodiment shown in Figure 2, the chemical absorbing liquid 5 of use amine etc., the secondary angry body 3 of the unstrpped gas that contains carbon dioxide is contacted at (for example about 50 ℃) near the normal temperature with chemical absorbing liquid 5, after chemical absorbing liquid 5 has absorbed carbon dioxide, this liquid is delivered to regenerator 7, when utilization heat medium 9 is heated to predetermined regeneration temperature (for example about 120 ℃), whole as the necessary heat of regeneration of chemical absorbing heat 5, utilize or apply flexibly steel plant produce 500 ℃ or following low-grade heat extraction (for example the heat extraction of sintering finished cooler etc.), from chemical absorbing liquid separates, separate and reclaim carbon dioxide 11.
Above-mentioned low-grade heat extraction can be used for heat medium 9 such as heating steam as described above and also can directly be used as heat medium 9, its utilization or the not special restriction of the form of applying flexibly.
In absorption tower 1, after chemical absorbing liquid 5 had absorbed carbon dioxide, secondary angry body 13 turned back to secondary angry body pipe arrangement 15, and the gas that acts as a fuel in the technology of the latter half etc. is used.In addition, extracted the chemical absorbing liquid of heated carbon dioxide, turned back to absorption tower 1 as regeneration absorption liquid 5 ' at regenerator 7.
In addition, in the present embodiment, whole as the necessary heat of regeneration of chemical absorbing liquid, expression be the example that utilizes or apply flexibly steel plant produce 500 ℃ or following low-grade heat extraction, and, in Fig. 4, describe about the example that the part of the necessary heat of regeneration of chemical absorbing liquid is utilized.
Secondly, in embodiment shown in Figure 3, use chemical absorbing liquid 5 such as amine, the secondary angry body 3 of the unstrpped gas that contains carbon dioxide is contacted at (for example about 50 ℃) near the normal temperature with chemical absorbing liquid 5, after chemical absorbing liquid has absorbed carbon dioxide, this liquid is delivered to regenerator 7, when utilization heat medium 9 is heated to predetermined regeneration temperature (for example about 120 ℃), according to the characteristic of chemical absorbing liquid, multistage ground (having 3 grades among Fig. 3) begins to apply flexibly 500 ℃ or the following suitable low-grade heat extraction that steel plant produce in the mode that the heat extraction temperature increases progressively from the lower heat extraction of temperature for the regeneration of chemical absorbing liquid.
That is to say, in the embodiment depicted in fig. 3, utilize or (for example apply flexibly the minimum low-grade heat extraction of temperature, blast furnace water quenching draining (about 90 ℃) etc.), the inferior low low-grade heat extraction of temperature (for example, sintering master discharging waste gas (about 280 ℃) etc.) and the highest low-grade heat extraction of temperature (for example, the heat extraction of sintering finished cooler (about 350 ℃) etc.), thus from chemical absorbing liquid, separate to reclaim carbon dioxide 11.
As mentioned above, above-mentioned 3 kinds of low-grade heat extractions can be applied flexibly successively in order to heat heat medium 9 such as heating steam, also can directly utilize its utilization or the not special restriction of the form of applying flexibly successively as heat medium 9.
In absorption tower 1, after chemical absorbing liquid 5 had absorbed carbon dioxide, secondary angry body 13 turned back to secondary angry body pipe arrangement 15, and the gas that acts as a fuel in the technology of the latter half etc. is used.In addition, extracted the chemical absorbing liquid of heated carbon dioxide, turned back to absorption tower 1 as regeneration absorption liquid 5 ' at regenerator 7.
In the present embodiment, why stipulate " according to the characteristic of chemical absorbing liquid ", be because according to the difference of the characteristic of the chemical absorbing liquid that uses, there is very big-difference in the necessary heat of regeneration of chemical absorbing liquid etc., the chemical absorbing liquid that also exists the serviceability temperature scope to be restricted, when the combination heat extraction, must fully take into account this point.About this point, in other embodiment, also preferably take in equally.
Moreover Fig. 4 is that expression is used for adopting chemical absorption method to separate the schematic diagram of the technology that reclaims carbon dioxide from the unstrpped gas that steel plant produce, and wherein applies flexibly the heat extraction that steel plant produce for the regeneration of chemical absorbing liquid, also applies flexibly factory's steam simultaneously.
In the embodiment depicted in fig. 4, use chemical absorbing liquid 5 such as amine, the secondary angry body 3 of the unstrpped gas that contains carbon dioxide is contacted at (for example about 50 ℃) near the normal temperature with chemical absorbing liquid 5, after chemical absorbing liquid has absorbed carbon dioxide, this liquid is delivered to regenerator 7, when utilization heat medium 9 is heated to predetermined regeneration temperature (for example about 120 ℃), regeneration for chemical absorbing liquid, utilize as far as possible or apply flexibly 500 ℃ or following low-grade heat extraction (for example coming from the heat extraction of sintering finished cooler etc.) that steel plant produce, simultaneously insufficient section uses factory with steam etc., reclaims carbon dioxide 11 thereby separate from chemical absorbing liquid.
In the present embodiment,, thereby can seek to reduce the necessary amount of factory with steam because 500 ℃ of using as far as possible that steel plant produce or following low-grade heat extraction are as described above.In addition, for convenience's sake, Fig. 4 shows the example that uses 1 grade of heat extraction that comes from sintering finished cooler etc. in 500 ℃ of producing in steel plant or the following low-grade heat extraction, but as shown in Figure 3, undoubtedly, also can be used multistagely or apply flexibly.
As mentioned above, above-mentioned low-grade heat extraction can be applied flexibly in heat mediums 9 such as heating heating steam, also can directly be used its utilization or the not special restriction of the form of applying flexibly as heat medium 9.
In addition, factory can directly apply flexibly as heating steam (heat medium 9) with steam etc., also can apply flexibly in heating heat medium 9.
In absorption tower 1, after chemical absorbing liquid 5 had absorbed carbon dioxide, secondary angry body 13 turned back to secondary angry body pipe arrangement 15, and the gas that acts as a fuel in the technology of the latter half etc. is used.In addition, extracted the chemical absorbing liquid of heated carbon dioxide, turned back to absorption tower 1 as regeneration absorption liquid 5 ' at regenerator 7.
As shown in Figure 3, in the present embodiment, why stipulate " trying one's best ", be because also produce following situation: after utilizing or apply flexibly all steel plant that can utilize or apply flexibly produce 500 ℃ or following low-grade heat extraction, the necessary heat of the regeneration of chemical absorbing liquid exists part not enough.
In this case, why stipulate to use factory's steam, be because in the steel plant at present the factories of a large amount of utilizations be the easiest and cheap with the use (migrating) of steam.
But the present invention does not get rid of the utilization of factory with the thermals source such as other heat extraction beyond the steam, and other heat extraction etc. just can be used fully as long as in the scope of not damaging purpose of the present invention.
In addition, the present invention is adopting chemical absorption method to separate in the technology that reclaims carbon dioxide, can utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce, the present invention ought to be not limited to the heating necessary energy of only utilizing or apply flexibly above-mentioned regenerator.
That is to say, preferably above-mentioned low-grade heat extraction is used as the heating necessary energy at the regenerator of the reason that plays a decisive role aspect the operating cost or applies flexibly, but the separation and recovery method of the carbon dioxide maximum and that popularize the most of exploitation at present is a chemical absorption method, is not subjected to the restriction of technological principle shown in Figure 1 (device constitutes).
In the technology that reality is used,,, also can utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce for these parts though in addition the degree of heating, also has the situation that needs heat exchange and heating not as regenerator.
Can be applicable to process for separating and recovering separation and recovery method, that use the carbon dioxide of chemical absorption method of the present embodiment, as long as satisfy " utilizing or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce " this important document, ought to be for technology without any special restriction.
Therefore, from the unstrpped gas (secondary angry body and burning and gas-exhausting thereof that steel plant produce) that contains carbon dioxide, use chemical absorbing liquid absorbing carbon dioxide, heat this absorption liquid afterwards and carry out the separation of carbon dioxide, in this technology, the kind of employed chemical absorbing liquid, its concentration and liquid measure, the device of this technology constitutes, conditions such as the temperature and pressure in this technology and various control methods etc., separation and recovery technology as the carbon dioxide that uses chemical absorption method has been a technique known, many improvement are also carried out, and the separation and recovery method of the present embodiment also comprises and can be suitable for these improvement technology.
In addition, these technology have been published in many known documents and patent gazette, so omit its detailed description at this.
(the secondary angry body after the carbon dioxide draw utilize method)
Though the secondary angry body heat difference of above-mentioned steel plant has all acted as a fuel and carried out heat utilization in factory.Wherein, from BFG, at first extract carbon dioxide, utilize again as process gas then, in this case, the following method of utilizing is arranged: the 1) fuel of gas turbine, 2) re-inject blast furnace and 3) be used for the semi-reduction process for making.
Above-mentioned 1) utilize in the method, the heating BFG make its heat from 750kcal/Nm 3Rise to 1000kcal/Nm 3, do not need to add auxiliary fuels such as light oil.In addition, above-mentioned 2) utilize in the method, by re-injecting blast furnace, this part helps to reach the reduction reaction of the iron of chemical balance to remove carbon dioxide, thereby can reduce the use amount as the coke of reducing agent.
In addition, adopt above-mentioned 3) utilize method, the leading portion use natural gas and coal in the past at blast furnace carries out in the technology of iron ore prereduction, by using this reducing gas, can cut down the use amount of natural gas and coal.
So, when after extracting carbon dioxide, utilizing again, compare, can show useful action effect with existing in-plant heat utilization as process gas.The advantage of these action effects is to be used effectively, and the fossil fuel that burns in air extracts carbon dioxide from resulting burning and gas-exhausting, and the exhaust of discharging into the atmosphere like this can not obtain described action effect in the past.
In addition, at upgrading COG and LDG and produce under the situation of hydrogen,, then may reduce the hydrogen manufacturing cost if extract unwanted carbon dioxide halfway.In addition, in factory, carry out under the situation of heat utilization in that COG and LDG are acted as a fuel, with from above-mentioned BFG, extract carbon dioxide after situation about utilizing again as process gas compare, can obtain same action effect.
(using method of separating the carbon dioxide that reclaims)
About the carbon dioxide that separate to reclaim, fixedly turning to purpose on a large scale, be stored in it in such ground of aquifer and exhausted gas field or marine research is serving as to lead to carry out with earth environment industrial technology research institution.In addition, to be the center, begun to carry out the utilization of EOR (oil pressure absorption method) and ECBM (coal buries the pressure absorption method of methane gas) abroad.In addition,, reclaim as the pressure of natural gas and to use even in the water-soluble natural gas field, also can injecting carbon dioxide and make it immobilization.
Wherein, fixedly turning on a large scale purpose, when in the ground of aquifer and exhausted gas field or during marine storage carbon dioxide, carbon dioxide is nugatory.So cost recovery is preferably cheap as far as possible.About this point, with from before the burning and exhausting in power plant separate recovery carbon dioxide compare, can separate the recovery carbon dioxide at an easy rate.
On the other hand, each steel plant produces the amount of carbon dioxide about 10,000 tons/year, and in the converter of steel plant, carbon dioxide can be used for the bottom blowing air port, the carbon dioxide that will separate recovery at present can be cut down emission amount of carbon dioxide with the carbon dioxide that the mode that circulates in the factory is used and buys from market to replace.
Secondly, the 2nd embodiment of the present invention relates to from carbon dioxide source and separates method and the device that reclaims carbon dioxide.
The separating and reclaiming device of carbon dioxide is to separate the device that reclaims carbon dioxide from carbon dioxide source, it is characterized in that: the formation that this device had is carbon dioxide absorption equipment: the gas absorbing carbon dioxide that contains carbon dioxide that is used for taking place from carbon dioxide the source; Absorbing medium reclaim equiment: be used for utilizing absorbing medium regeneration field thermal source separating carbon dioxide with the regeneration absorbing medium from the absorbing medium that has absorbed carbon dioxide; The carbon dioxide absorption medium: the pumped (conveying) medium as carbon dioxide circulates at two equipment rooms; And send pipe arrangement and return pipe arrangement: be used for the transport of carbon dioxide absorbing medium; Wherein, above-mentioned carbon dioxide absorption equipment is arranged near the carbon dioxide generation source, and above-mentioned absorbing medium reclaim equiment is arranged on and carbon dioxide generation different place, residing place, source.
In addition, the separation and recovery method of carbon dioxide is to separate the method that reclaims carbon dioxide from carbon dioxide generation source, it is characterized in that: adopt the carbon dioxide absorption equipment that is provided with near carbon dioxide generation source, utilize carbon dioxide absorption medium absorbing carbon dioxide from the gas of supplying with by this carbon dioxide generation source that contains carbon dioxide, utilize regeneration of absorption solution to heat this carbon dioxide absorption medium with thermal source afterwards, employing makes carbon dioxide separation with the regeneration of absorption solution equipment that carbon dioxide absorption equipment is in different places.
In the embodiment of this separation and recovery method and device, the source takes place and absorbs heat regeneration thermal source in the carbon dioxide that is in different places by combination, can be effectively and separate at an easy rate and reclaim carbon dioxide.
For example, thermal power plant (carbon dioxide generation source) and the heat extraction source in the steel plant (absorbing heat regeneration thermal source) by bordering compounding can make the possibility that is separated into than more cheap in the past carbon dioxide.
The present embodiment is the same with the 1st embodiment, can adopt chemical absorption method, but this is not had any restriction, also can use the separation and recovery method that needs other hot carbon dioxide.As separation and recovery method, preferably therefore chemical absorption method, will describe along this line of chemical absorption method below.In addition, the utilization accompanying drawing describes the present embodiment in detail, but the present embodiment is not limited to illustrated content.
Fig. 5~Fig. 9 represents is the source to take place and absorb heat regeneration thermal source and separate the device (technology) that reclaims carbon dioxide by the carbon dioxide that combination is in different places.In addition, in these figure, the constitutive requirements about same device etc. identify same symbol, after Fig. 6, for fear of repetition, also omit its explanation sometimes.
As shown in Figure 5, the present embodiment from CO 2Recovery CO is separated in the generation source 2The formation that had of device 50 be CO 2Absorption equipment 55: be used for from by CO 2Generation source 53 is by the CO that contains of pipe arrangement supply 2Gas in adopt CO 2Absorbing medium 57 absorbs CO 2Absorbing medium reclaim equiment 61: be used for utilizing absorbing medium regeneration to use thermal source 63 separating carbon dioxides with the regeneration absorbing medium from the absorbing medium 57 that has absorbed carbon dioxide; CO 2Absorbing medium 57: as the pumped (conveying) medium of carbon dioxide at CO 2Absorption equipment 55 and CO 2Circulate between the absorption equipment 55; And send pipe arrangement 59 and return pipe arrangement 65: be used for transport of carbon dioxide absorbing medium 57; Wherein, above-mentioned CO 2Absorption equipment 55 be arranged on CO 2Near the generation source 53, and above-mentioned absorbing medium reclaim equiment 61 is provided with and carbon dioxide generation different place, 53 residing places, source.
Therefore, use said apparatus 51 the present embodiment from CO 2Recovery CO is separated in the generation source 2Method circulate in the following way, promptly adopt near CO 2The CO in generation source 2Absorption equipment 55, from by this CO 2Generation source 53 is supplied with contains CO 2Gas in, use at CO 2The CO that circulates between absorption equipment 55 and the regeneration of absorption solution equipment 61 2 Absorbing medium 57 is as CO 2Pumped (conveying) medium 57 absorb CO 2Afterwards, by being used for CO 2The pipe arrangement 59 of sending of the conveying of absorbing medium 57 is delivered to regeneration of absorption solution equipment 61, utilizes thermal source 63 these CO of heating of absorbing medium regeneration usefulness 2Absorbing medium 57 adopts and CO 2The regeneration of absorption solution equipment 61 that the generation source is in different places makes CO 2Separate, by being used for CO 2The pipe arrangement 65 that returns of the conveying of absorbing medium 57 turns back to CO 2Absorption equipment 55.
(factory that separation and recovery method of the present embodiment and device may be suitable for)
As the factory that the separation and recovery method of the present embodiment and device can be suitable for, can list and have extensive CO 2The steel plant in generation source, thermal power plant, cement plant etc., but also the present invention ought to be not limited to these.
The present embodiment also can be applicable to the extensive CO that has beyond the steel plant that illustrate in the 1st embodiment 2The factory in generation source.
For example, source (for example thermal power plant) and regeneration of absorption solution thermal source (closing on the heat extraction that other factory in thermal power plant produces) take place in the carbon dioxide that is in different places by combination, can be effectively and the separation and recovery method of the present embodiment is provided at an easy rate.
(carbon dioxide generation source)
The source takes place as the said carbon dioxide of the present embodiment, the same with the 1st embodiment, the pipe arrangement etc. that is equivalent in above-mentioned factory, to produce the equipment of carbon dioxide and is transported to subsequent processing from the gas that this equipment will contain carbon dioxide.
In addition, under the situation of discharging not being transported to subsequent processing, exhaust apparatus (chimney etc.) is included among the carbon dioxide generation source.As the equipment that produces above-mentioned carbon dioxide, steel plant are example with the blast furnace associating, and what adapt with it is blast furnace, coke oven, converter etc., and in the cement plant, for example cement rotary kiln etc. adapts with it, but the present invention can not be defined in this at all.
In addition, as pipe arrangement, be example with blast furnace associating steel plant, blast furnace gas (BFG) pipe arrangement, oven gas (COG) pipe arrangement, converter gas (LDG) pipe arrangement etc. adapt with it, but the present invention can not be defined in this at all.
(gas (unstrpped gas) that contains carbon dioxide)
The said gas that contains carbon dioxide of the present embodiment, can be the gas that contains carbon dioxide that produces by carbon dioxide generation source, for example under the situation of above-mentioned steel plant, although difference according to the difference of its formation and to some extent, but with blast furnace associating steel plant is example, be blast furnace gas (BFG), oven gas (COG), converter gas secondary angry bodies (unburned gas) such as (LDG), in addition, also comprise the gas (process gas) that to produce hydrogen be purpose, produce in the process (technology) of the angry bodies of above-mentioned pair such as upgrading COG and LDG.
In the present embodiment, also can be with the burning and gas-exhausting of the angry body of above-mentioned pair as the gas that contains carbon dioxide (unstrpped gas).In addition, in the cement plant, for example suspended preheater (suspension preheater) exit gas, electrostatic (electric dust) precipitator exit gas etc. adapt with it, and the burning and gas-exhausting in thermal power plant etc. adapts with it, but the present invention can not be defined in this at all.
When unstrpped gas (carbon dioxide generation source produce secondary angry body or its burning and gas-exhausting) can be used as high-grade heat extraction when being used, then in the present invention, these gases are used after finishing as the utilization of high-grade heat extraction again, because the temperature when adopting the chemical absorption method absorbing carbon dioxide can be near the temperature the normal temperature.
Unstrpped gas can reclaim a kind of separation of supplying with carbon dioxide wherein individually, also can mix two or more.In the mixed style of two or more, except that the burning and gas-exhausting mixed style each other of each other mixed style of secondary angry body, secondary angry body, also comprise the burning and gas-exhausting of secondary angry body and the mixed style of secondary angry body.
That is to say, in the present embodiment, a plurality of carbon dioxide absorption equipment are set, can handle plurality of raw materials gas near a plurality of carbon dioxide generations source.
In unstrpped gas, about the CO of BFG, COG, LDG 2Concentration and the 1st embodiment explanation identical, so omit its explanation at this.
The CO of the gas of the suspended preheater outlet that produces in the cement plant 2Concentration be about 14 volume %, the CO of the gas of electrostatic (electric dust) precipitator outlet 2Concentration be about 9 volume %.Moreover, the CO of the burning and gas-exhausting that the thermal power plant produces 2Concentration be about several~more than 10 volume %.
The present embodiment also can be suitable for any unstrpped gas in them.As unstrpped gas, the unstrpped gas that preferably carbon dioxide concentration is high be we can say, uses burning and gas-exhausting, the burning and gas-exhausting of COG, the burning and gas-exhausting of LDG and the mist of these gas and other gas of BFG, BFG all to be fine.
Moreover, as the back narrate, also can be useful in upgrading COG and LDG and produce the gas that produces in the process of hydrogen.When means such as utilization chemical absorption method from the high unstrpped gas of these gas concentration lwevels are separated the recovery carbon dioxide, can obtain the action effect same with the explanation of the 1st embodiment.
CO 2Absorbing medium can use the same absorbing medium of chemical absorbing liquid with the explanation of the 1st embodiment, ought to have no particular limits.
As the carbon dioxide absorption equipment that is used for absorbing carbon dioxide, can use the same absorption equipment in absorption tower that illustrates with the 1st embodiment, the present invention ought to not can be defined in this especially.
As be used for from the absorbing medium that has absorbed carbon dioxide utilize absorbing medium regeneration with the thermal source separating carbon dioxide absorbing medium reclaim equiment of the absorbing medium of regenerating, can use the same reclaim equiment of regenerator that illustrates with the 1st embodiment, but the present invention ought to not can be defined in this especially.
For the transport of carbon dioxide absorbing medium makes it to circulate between carbon dioxide absorption equipment and absorbing medium reclaim equiment, send pipe arrangement and return pipe arrangement and be arranged between this two equipment.
Thermal source is used in regeneration as absorbing medium, preferably uses the technical process heat extraction.Specifically, be the heat extraction that produces in the heat extraction that produces in the iron-smelting process or the cement manufacturing process, be to be preferably 500 ℃ or following, 400 ℃ or following low-grade heat extraction more preferably, but the present invention ought to not can be confined to this.Wherein, about the heat extraction that in iron-smelting process, produces, because identical with the 1st embodiment explanation, thereby omit its explanation at this.
As the heat extraction that produces in the cement manufacturing process, for example can list exhaust (about 380 ℃), slag cooler (clinker cooler) exhaust (about 350 ℃), the electrostatic (electric dust) precipitator outlet exhaust (about 200 ℃) of suspended preheater, but the present invention ought to not can be defined in this.
In the present embodiment, thermal source is used in regeneration as absorbing medium, and the situation of partly utilizing or apply flexibly the combustion heat of fuel is also included within the technical scope of the present invention.
Thermal source is used in regeneration as absorbing medium, for example can list sintering finished cooler, hot-blast stove, blast furnace water quenching slag cooling device and sintering furnace etc. (with reference to concrete example 1~5 described later) in iron-smelting process; In cement manufacturing process, for example can list suspended preheater, clinker cooler and electrostatic (electric dust) precipitator etc., but the present invention can not be defined in this at all.
That is to say that the present embodiment with thermal source (part or all), is preferably used technical process heat extraction 63a as regeneration of absorption solution as shown in Figure 6.
This be because: illustrated as the 1st embodiment, be difficult to by low-grade heat energy of steel plant and cement plant utilization (in low-grade heat energy by utilizing or applying flexibly, the preferred heat energy that utilizes as far as possible or apply flexibly high temperature), can reduce the separation cost recovery of carbon dioxide significantly.
In addition, as the regeneration of absorption solution thermal source, why preferred 500 ℃ or following low-grade heat extraction is based on the same reason of the 1st embodiment explanation.
In the present embodiment, as the regeneration of absorption solution thermal source, can utilize or apply flexibly a kind of thermal source separately, also can utilize or apply flexibly two or more thermals source simultaneously.When and when heat medium being heated to predetermined temperature with heat extraction, for example also two or more heat extractions can be begun to heat heat medium in the mode that the heat extraction temperature increases progressively from the lower heat extraction of temperature.At this moment, if last heat energy deficiency also can be burnt with fuel.
That is to say, the present embodiment may not be subject to and adopt chemical absorption method to separate the situation of only utilizing or apply flexibly the technical process heat extraction in the technology that reclaims carbon dioxide, for example in iron-smelter except the our factory consume, the present embodiment also can be with the part of the fuel gas sold as domestic gas etc. as auxiliary fuel.Explanation among Fig. 2~Fig. 4 of such example and the 1st embodiment is identical, so omit its explanation at this.
Secondly, the present embodiment is characterised in that: above-mentioned carbon dioxide absorption equipment be arranged on above-mentioned carbon dioxide take place the source near, above-mentioned absorbing medium reclaim equiment is arranged on and different place, residing place, source takes place carbon dioxide.
The present invention as absorbing medium, therefore, even the pipe arrangement distance is longer, carries the power of this medium to compare with unstrpped gas (gas) chemical absorbing liquid, also is few utterly.On the other hand, keep clear of carbon dioxide at carbon dioxide absorption equipment and the source takes place and be arranged under the situation (situation about leaving) of different places, for unstrpped gas is supplied with CO 2Absorption equipment, unstrpped gas supplying tubing be apart from lengthening, and transport this pumped (conveying) medium and be the power of gas and compare with the situation of carrying liquid, be big utterly.
As with carbon dioxide the place that is provided with that the different absorbing medium reclaim equiment in place is set in source takes place, specifically, preferably absorbing medium regeneration with thermal source near.This be because: the pipe arrangement that thermal medium (technical process waste gas and burning gases etc.) is transported to the absorbing medium reclaim equiment with thermal source from absorbing medium regeneration can prevent to occur the low of the decrease of temperature and the thermal efficiency by this apart from lengthening in the thermal medium course of conveying.
That is to say, source and absorbing medium regeneration thermal source phase time take place in the carbon dioxide that is in different places when combination, by making carbon dioxide absorption equipment the source take place near carbon dioxide, can shorten with absorbing medium (absorption liquid) fed distance of comparing, needing the unstrpped gas pipe arrangement of very big transmitting power, absorbing medium (absorption liquid) is carried between the carbon dioxide absorption equipment of different places and absorbing medium reclaim equiment, can be effectively and separate at an easy rate and reclaim carbon dioxide.
In addition, the source takes place, carry thermal medium to compare from the absorbing medium regeneration that is in different places with thermal source near carbon dioxide with the absorbing medium reclaim equiment, the absorbing medium reclaim equiment can be shortened by pipe arrangement significantly near the absorbing medium regeneration thermal source that is in different places carry the distance of regeneration with the thermal medium of thermal source, the temperature that can suppress thermal source descends, can be effectively and separate at an easy rate and reclaim carbon dioxide.
Specifically, the relational expression (for example with reference to Figure 10~14) of A<C and B<C is preferably satisfied in the distance A between above-mentioned carbon dioxide generation source and the carbon dioxide absorption equipment, absorbing medium reclaim equiment and absorbing medium regeneration with the distance C apart between B and carbon dioxide absorption equipment and the absorbing medium reclaim equiment between the thermal source.
At this, be that its explanation is same as described above under 1 pair 1 the situation of relation at carbon dioxide absorption equipment and absorbing medium reclaim equiment; More than 1 pair, many to 1 and the situation of multi-to-multi under, between separately carbon dioxide absorption equipment and absorbing medium reclaim equiment, preferably all satisfy above-mentioned relation.
In addition, as absorbing medium regeneration thermal source, under the situation of the multistage technical process heat extraction that the different temperatures level is set, the distance between the thermal source that absorbing medium reclaim equiment and temperature levels is the highest is set at B (for example with reference to Figure 12 and 14).
More particularly, be used for the source taking place and supply with sending the pipe arrangement distance Y and returning pipe arrangement of the pipe arrangement distance X of the gas that contains carbon dioxide, above-mentioned carbon dioxide absorption medium apart from Z to carbon dioxide absorption equipment from above-mentioned carbon dioxide, preferably satisfy the relational expression of 2X<(Y+Z), furtherly, if will be used for being set at W with thermal source to the pipe arrangement distance of absorbing medium reclaim equiment heat supply (for example burning and gas-exhausting of technical process exhaust and fuel), then more preferably satisfy the relational expression of (X+W)<(Y+Z) from absorbing medium regeneration.
At this moment, as absorbing medium regeneration thermal source, under the situation of the multistage technical process heat extraction that the different temperatures level is set, the distance between the thermal source that absorbing medium reclaim equiment and temperature levels is the highest is set at W (for example with reference to Figure 12 and 14).
The present embodiment also can possess one or more carbon dioxide absorption equipment and one or more regeneration of absorption solution equipment.For example, there are being a plurality of carbon dioxide to take place under the situation in source, also can the source taking place carbon dioxide absorption equipment is set respectively near a plurality of carbon dioxide.Equally, belong under the situation of a plurality of positions can be used as the technical process heat extraction that absorbing medium regeneration is used with thermal source, also can with thermal source the absorbing medium reclaim equiment be set respectively near a plurality of absorbing mediums regeneration.
That is to say, carbon dioxide absorption equipment and regeneration of absorption solution equipment can obtain 1 pair 1, many to 1, any relation of multi-to-multi, about regeneration of absorption solution equipment, the heat of absorbing medium regeneration with thermal source pooled together, say it is preferred from installation cost and operating cost this point.
For example, as shown in Figure 7, as many to 1 example, near 2 carbon dioxide generation source 53a and 53b 2 carbon dioxide absorption equipment 55a and 55b are set respectively, independently send pipe arrangement 59a and return pipe arrangement 65a and send pipe arrangement 59b and return pipe arrangement 65b and be arranged on different places separately, specifically be arranged on 2 carbon dioxide absorption equipment and 1 regeneration of absorption solution equipment 61 being provided with near regeneration thermal source 63 between.
Fig. 7 represents be with 2 systems independently mode form the example of sending pipe arrangement and returning pipe arrangement, but, also can make the pipe arrangement of 2 systems accumulate 1 system halfway, absorbing medium 57 is transported to 1 regeneration of absorption solution equipment 61, when turning back to 2 carbon dioxide absorption equipment 55a and 55b, be divided into 2 systems.
In addition, wantonly 1 about carbon dioxide absorption equipment and regeneration of absorption solution equipment is set to a plurality of situations, for example, as shown in Figure 8, as the example of multi-to-multi, the carbon dioxide absorption equipment 55a~55c that is provided with near 3 carbon dioxide generation source 53a~53c is arranged on different places separately respectively, specifically, close regeneration thermal source 63a and 63b separately is provided with absorbing medium reclaim equiment 61a and 61b.
Send pipe arrangement and return pipe arrangement as what between two equipment of this situation, be provided with, also can make 3 of being connected 3 carbon dioxide absorption equipment 55a~55c one sides send pipe arrangement 59a~59c each other and return pipe arrangement 65a~65c and compile halfway each other, via reallocation, send pipe arrangement 59d~59e and return pipe arrangement 65d~65e as 2, be connected on each absorbing medium reclaim equiment 61a~61b.
At this moment, at 3 desired CO of carbon dioxide absorption equipment 2Absorbability, the CO in the handled unstripped gas scale of construction of each carbon dioxide absorption equipment and this gas for example 2Under the respectively different situation of concentration, send pipe arrangement 59a~59c and return the pipe arrangement diameter (area) of pipe arrangement 65a~65c and the conveying capacity of delivery pump etc. in order to supply with corresponding absorbing medium amount, can to adjust.
Specifically, at each carbon dioxide absorption equipment 55a: the carbon dioxide absorption amount of 55b: 55c is under 5: 3: 2 the situation, for example can make to send pipe arrangement 59a: 59b: 59c (return pipe arrangement 65a: 65b: 65c) pipe arrangement area or conveying capacity also become 5: 3: 2.
Similarly, in the power of regeneration of 2 absorbing medium reclaim equiments, for example under the utilizable absorbing medium of each the absorbing medium reclaim equiment regeneration situation different with thermal source etc., in order to supply with corresponding absorbing medium amount, can adjust pipe arrangement diameter (area) and conveying capacity.
Specifically, be under 6: 4 the situation at the heat of the absorbing medium regeneration usefulness of supplying with each absorbing medium reclaim equiment 61a: 61b, for example can make and send pipe arrangement 59d: 59e (return pipe arrangement 65d: 65e) pipe arrangement area or conveying capacity also become 6: 4.
In addition, in the present embodiment, with thermal source (part or all), the technical process heat extraction of different temperatures level can be set multistagely also as regeneration of absorption solution.This and identical (with reference to Fig. 3) of the 1st embodiment explanation.
In addition, in arbitrary scheme of the 1st embodiment and the present embodiment, utilize the heating of regeneration of absorption solution with thermal source heating absorbing medium, be not limited to directly heat the heating of the absorbing medium in the absorbing medium reclaim equiment, also can send the technical process heat extraction that the different temperatures level is set on pipe arrangement and the absorbing medium reclaim equiment multistagely, absorbing medium is heated.
At this moment, as shown in Figure 9, preferably begin to utilize heat extraction in the mode that the heat extraction temperature increases progressively from the lower technical process heat extraction of temperature.In other words, when being dispersed in as these thermals source that regeneration is used with thermal source a plurality of local time, as shown in Figure 9, can being directed near these thermals source and being used with thermal source sending pipe arrangement as regeneration.
At this moment, can begin to utilize heat extraction from the lower technical process heat extraction of temperature in the mode that the heat extraction temperature increases progressively, be configured according to order, send pipe arrangement by near the thermal source so that make from the lower thermal source established technology process heat extraction 63a (heat source temperature T1) of temperature to the higher thermal source established technology process heat extraction 63b (heat source temperature T2) of temperature.
In addition, near the highest thermal source established technology process heat extraction 63c (heat source temperature T3) of temperature, absorbing medium reclaim equiment 61 is set.At this, T1<T2<T3.Thus, in the process that absorption liquid passes through in sending pipe arrangement 59, this absorbing medium is preheating to high temperature at leisure and sends into absorbing medium reclaim equiment 61, regenerates necessary heat and the separation of carbon dioxide is carried out at this.
The absorbing medium that passes through in sending pipe arrangement is generally liquid, but as top narrate, send under the situation of pipe arrangement utilizing thermal source heating, sometimes may partly vaporize or contain under the gas state of (comprising the carbon dioxide of from absorbing medium, separating in this gas) at absorbing medium and carry, but consider from the angle that reduces transmitting power, as carrying pipe arrangement heating thermal source, preferably remain under such temperature, so that can not make absorbing medium take place to vaporize or can not make carbon dioxide separation.
In other words, preferably higher as absorbing medium than simple gas density, particularly preferably be liquid.As long as transmitting power is not being produced in the scope of significant impact, liquid also can comprise a part of solid or gas.
In addition, in arbitrary scheme of the 1st embodiment and the present embodiment, also can on returning pipe arrangement, utilize Cooling and Heat Source to return absorbing medium in the pipe arrangement with cooling.That is to say that the absorbing medium that returns in the pipe arrangement was cooled to lower temperature before being back to carbon dioxide absorption equipment, this absorption efficiency this point from carbon dioxide considers it is preferred.
As shown in Fig. 1~4 of the 1st embodiment, usually cool off in such a way, promptly and send between the absorbing medium in the pipe arrangement and carry out heat exchange, but in steel plant or other large-scale factory, sometimes use a large amount of Cooling and Heat Source, also may utilize a part sometimes.
But, because carbon dioxide absorption equipment of the present invention is in different place (place of leaving) with the absorbing medium reclaim equiment, so by putting near cold can being cooled to the ambient temperature naturally.Therefore, under ambient temperature condition with higher such as summer, it is effective especially utilizing above-mentioned Cooling and Heat Source.
It more than is the explanation of the present embodiment.Below use the Brief Description Of Drawings concrete example, but the present invention can not be defined in this at all.
Figure 10~13 schematically illustrate the carbon dioxide that is in different places by combination and the source takes place separate the concrete example that reclaims carbon dioxide with the regeneration of absorption solution thermal source.
In addition, in these accompanying drawings, with regard to same constitutive requirements marks such as device same symbol, thereby after Figure 11,, sometimes its explanation is omitted for fear of repetition.
(concrete example 1)
The formation of carbon dioxide separation retracting device 100 shown in Figure 10 comprises:
CO 2Absorption equipment (also abbreviating the absorption tower sometimes as) 95, it is used for (the CO from BFG 2Concentration is 20~25 volume %) the middle CO that adopts 2Absorbing medium 97 absorbs CO 2, wherein, BFG contains CO 2Gas, this gas is by as CO 2The BFG in generation source is responsible for 93 and supplies with by pipe arrangement 94;
Absorbing medium reclaim equiment (regenerator 101), it is used for from having absorbed CO 2Absorbing medium 97 in to utilize absorbing medium regeneration be sinter cooler heat extraction (250~350 ℃) separation of C O with thermal source 2With regeneration absorbing medium 97;
Absorbing medium 97, it is as CO 2Pumped (conveying) medium between absorption tower 95 and regenerator 101, circulate; And
Send pipe arrangement 99 and return pipe arrangement 105, it is used to carry absorbing medium 97;
Wherein, above-mentioned absorption tower 95 be arranged on BFG be responsible for 93 near, and above-mentioned regenerator 101 is arranged on BFG and is responsible for different place, 93 residing places, in more detail, is arranged on as absorbing medium regeneration with near the sinter cooler 103a of thermal source.
Therefore, use the CO of said apparatus 100 2Separation and recovery method, adopt and to be responsible for 93 absorption tower 95 near BFG, utilize as CO 2 The absorbing medium 97 that pumped (conveying) medium circulates between absorption tower 95 and regenerator 101 absorbs CO from being responsible for 93 BFG that supply with by BFG 2, send pipe arrangement 99 by what be used to carry absorbing medium 97 afterwards, this absorbing medium 97 is delivered to regenerator 101, utilize the sinter cooler heat extraction to heat this absorbing medium 97 again, adopt and be responsible for 93 regenerators 101 that are in different places with BFG and make CO 2Separate, in addition recycling by being used to carry the returning that pipe arrangement 105 turns back to the absorption tower of absorbing medium 97 then.
At this, be used for supplying with distance X=BFG person in charge 93 of the pipe arrangement 94 of BFG and the distance A between the absorption tower 95 to absorption tower 95 from the BFG person in charge 93, be used for from sinter cooler 103a supply with to regenerator 101 between the distance W=sinter cooler 103a of pipe arrangement 96 of sinter cooler heat extractions and the absorption tower 95 apart from B, send the distance Y of pipe arrangement 99=return pipe arrangement 105 apart from the distance C between Z=absorption tower 95 and the regenerator 101, their constituent relation satisfies any one relational expression among 2X<(Y+Z), (X+W)<(Y+Z) and A<C and the B<C.
The BFG that blast furnace produces is responsible for the gas that acts as a fuel by BFG and supplies with in the steel plant oneself power plant or near thermal power plant, and at this, favourable a bit is, on BFG is responsible for valve is set, and part or all of BFG passed through CO 2After separating and reclaiming device 100 is removed carbon dioxide, can be used as the high fuel of efficiency of combustion and be supplied to oneself power plant or thermal power plant (this point can obtain the same effect with the explanation of the 1st embodiment).
(concrete example 2)
CO shown in Figure 11 2What separating and reclaiming device 110 was used with thermal source as absorbing medium regeneration is hot-blast stove exhaust (150~300 ℃) (part or all), regenerator 101 is arranged on as near the hot-blast stove 103b of absorbing medium regeneration usefulness thermal source, formation in addition and CO shown in Figure 10 2Separating and reclaiming device 100 is same.
Therefore, use the CO of said apparatus 110 2Separation and recovery method, except utilizing hot-blast stove exhaust heating absorbing medium 97 this point, the CO that all the other are shown in Figure 10 with employing 2The CO of separating and reclaiming device 100 2Separation and recovery method is the same.
At this, distance A between the distance X of pipe arrangement 94=BFG person in charge 93 and the absorption tower 95, be used for from hot-blast stove 103b supply with to regenerator 101 between the distance W=hot-blast stove 103b of pipe arrangement 96 of hot-blast stove exhausts and the absorption tower 95 apart from B, send the distance Y of pipe arrangement 99=return pipe arrangement 105 apart from the distance C between Z=absorption tower 95 and the regenerator 101, their constituent relation satisfies any one relational expression among 2X<(Y+Z), (X+W)<(Y+Z) and A<C and the B<C.
(concrete example 3)
CO shown in Figure 12 2Separating and reclaiming device 120 is examples that the technical process heat extraction of different temperatures level is set with part or all of thermal source, multistage ground (2 grades) as regeneration of absorption solution.
Use in the thermal source in absorbing medium regeneration, as the high thermal source of temperature levels, utilize hot-blast stove exhaust (150~300 ℃) (part or all), in addition, as the low thermal source of temperature levels, utilize blast furnace water quenching slag draining (60~90 ℃), regenerator 101 be arranged on absorbing medium regeneration with thermal source be hot-blast stove 103b near, send pipe arrangement 99 to be configured by the mode near the position of blast furnace water quenching slag cooling device, except that this point, remaining constitutes and CO shown in Figure 10 2Separating and reclaiming device 100 is same.
Therefore, adopt the CO of said apparatus 120 2Separation and recovery method at first utilizes blast furnace water quenching slag draining heating (preheating) to send absorbing medium 97 in the pipe arrangement 99, utilizes hot-blast stove exhaust heating absorbing medium 97 afterwards, and except that this point, remaining constitutes and CO shown in Figure 10 2Separating and reclaiming device 100 is same.
At this, distance A between the distance X of pipe arrangement 94=BFG person in charge 93 and the absorption tower 95, be used for from hot-blast stove 103b supply with to regenerator 101 between the distance W=hot-blast stove 103b of pipe arrangement 96 of hot-blast stove exhausts and the absorption tower 95 apart from B, send the distance Y of pipe arrangement 99=return pipe arrangement 105 apart from the distance C between Z=absorption tower 95 and the regenerator 101, their constituent relation satisfies any one relational expression among 2X<(Y+Z), (X+W)<(Y+Z) and A<C and the B<C.
(concrete example 4)
CO shown in Figure 13 2The formation of separating and reclaiming device 130 is, from as CO 2Oneself power plant in the steel plant in generation source (joint fires power plant) 93a supplies with to absorption tower 95 by pipe arrangement 94a and contains CO 2Burning of gas exhaust (CO 2Concentration 8~20 volume %), except that this point, remaining constitutes and CO shown in Figure 10 2Separating and reclaiming device 100 is same.
Therefore, use the CO of said apparatus 130 2Separation and recovery method adopts the absorption tower 95 near oneself power plant 93a in the steel plant, uses absorbing medium 97 to absorb CO from the burning and gas-exhausting that oneself power plant 93a supplies with by this 2, except that this point, the CO that all the other are shown in Figure 10 with use 2The CO of separating and reclaiming device 100 2Separation and recovery method is identical.
At this, distance A between the distance X of pipe arrangement 94a=oneself power plant 93a and the absorption tower 95, be used for from sinter cooler 103a supply with to regenerator 101 between the distance W=sinter cooler 103a of pipe arrangement 96 of sinter cooler exhausts and the absorption tower 95 apart from B, send the distance Y of pipe arrangement 99=return pipe arrangement 105 apart from the distance C between Z=absorption tower 95 and the regenerator 101, their constituent relation satisfies any one relational expression among 2X<(Y+Z), (X+W)<(Y+Z) and A<C and the B<C.
In addition, oneself power plant can or adopt the CO of Figure 10~12 with BFG in the steel plant 2BFG and heavy oil that separating and reclaiming device is removed carbon dioxide are that fuel carries out thermal power generation.The CO of above-mentioned burning and gas-exhausting 2Concentration is the examples of 8~20 volume % when being to use common BFG and heavy oil.
(concrete example 5)
CO shown in Figure 14 2The formation of separating and reclaiming device 140 is, from as CO 2The thermal power plant 93b in generation source (near steel plant) supplies with to absorption tower 95 by pipe arrangement 94a and contains CO 2Burning of gas exhaust (CO 2Concentration 8~15 volume %), and as the regeneration of absorption solution thermal source, be the example of the technical process heat extraction of multistage (3 grades) steel plant that the different temperatures level is set.
Use in the thermal source in absorbing medium regeneration, as the highest thermal source of temperature levels, utilize sinter cooler heat extraction (250~350 ℃), as temperature levels time high thermal source, utilize hot-blast stove exhaust (150~300 ℃) (part or all), in addition, as the lower thermal source of temperature levels, utilize blast furnace water quenching slag cooling water (60~90 ℃), regenerator 101 is arranged on the place different with thermal power plant 93b, in detail, be arranged on as absorbing medium regeneration with near the sinter cooler 103a of thermal source, send pipe arrangement 99 to be configured by the mode near the position of blast furnace water quenching slag cooling device 103c and hot-blast stove 103b, except that this point, remaining constitutes and CO shown in Figure 10 2Separating and reclaiming device 100 is same.
Therefore, use the CO of said apparatus 140 2Separation and recovery method adopts near the absorption tower 95 of adjoining the thermal power plant 93b of steel plant, uses absorbing medium 97 to absorb CO from the burning and gas-exhausting of being supplied with by this thermal power plant 93b 2And then begin to utilize heat extraction in the mode that the heat extraction temperature increases progressively from the lower technical process heat extraction of temperature, at first utilize the draining of blast furnace water quenching slag, then utilize hot-blast stove exhaust heating (preheating) to send absorbing medium 97 in the pipe arrangement 99, utilize sinter cooler heat extraction heating absorbing medium 97 afterwards, except that this point, the CO shown in Figure 10 with use 2The CO of separating and reclaiming device 100 2Separation and recovery method is identical.
At this, distance A between the distance X of pipe arrangement 94b=thermal power plant 93b and the absorption tower 95, be used for from sinter cooler 103a supply with to regenerator 101 between the distance W=sinter cooler 103a of pipe arrangement 96 of sinter cooler heat extractions and the absorption tower 95 apart from B, send the distance Y of pipe arrangement 99=return pipe arrangement 105 apart from the distance C between Z=absorption tower 95 and the regenerator 101, their constituent relation satisfies any one relational expression among 2X<(Y+Z), (X+W)<(Y+Z) and A<C and the B<C.
In addition, the process for separating and recovering (device and method) that can be suitable for as the present embodiment, use the carbon dioxide of chemical absorption method, as long as satisfy near above-mentioned " carbon dioxide absorption equipment be arranged on carbon dioxide takes place the source, above-mentioned absorbing medium reclaim equiment is arranged on and different place, residing place, source takes place carbon dioxide " this important document, then ought to have no particular limits.
Therefore, from the unstrpped gas (secondary angry body and burning and gas-exhausting thereof that steel plant produce) that contains carbon dioxide, use chemical absorbing liquid absorbing carbon dioxide, heat this absorption liquid afterwards and carry out the separation of carbon dioxide, in this technology, condition such as the device of the kind of employed chemical absorbing liquid, its concentration and liquid measure, this technology constitutes, the temperature and pressure in this technology and various control methods etc., separation and recovery technology as the carbon dioxide that uses chemical absorption method has been a technique known, and many improvement are also in progress.
Much less, the present embodiment also comprises these improvement technology, can be used as process for separating and recovering, and but, these technology are published in many known documents and patent gazette, so omit its detailed description at this.
(the secondary angry body after the carbon dioxide draw utilize method)
About the method for utilizing of the secondary angry body after the carbon dioxide draw, identical with the 1st embodiment explanation is so omit its explanation at this.
(unstrpped gas after the carbon dioxide draw utilize method)
About the unstrpped gas after the carbon dioxide draw, can equally with the secondary angry body of steel plant be used for cement plant beyond steel plant and thermal power plant, then can be used, and for unavailable, then will not utilize and discharge (with reference to Figure 13 and 14).
(using method of separating the carbon dioxide that reclaims)
About the using method of the carbon dioxide that separate to reclaim, identical with the explanation of the 1st embodiment is so omit its explanation at this.
As mentioned above, according to the 1st embodiment of the present invention, can obtain following effect.
1) compares with the burning and gas-exhausting in thermal power plant, from the secondary angry body (unburned gas) of the higher steel plant of carbon dioxide ratio, adopt chemical absorption method to separate and reclaim carbon dioxide, can make the separation reclaimer become compact thus.Though also depend on the unstrpped gas of use, for instance, if with the BFG of steel plant as unstrpped gas to replace the low burning and gas-exhausting of gas concentration lwevel of Coal-fired power plant, then cost of equipment can reduce by 3 one-tenth or more than.
2) by utilizing or apply flexibly 0~500 ℃ of steel plant, be preferably 350 ℃ or following low-grade energy, can reduce the operating cost that the carbon dioxide separation that adopts chemical absorption method reclaims.Specifically, in the employed regenerator of chemical absorption method, heating chemical absorbing liquid necessary energy becomes this method at the reason that plays a decisive role aspect the operating cost (about 5~8 one-tenth), at this, because can utilize or apply flexibly the low-grade heat extraction in the steel plant, so can reduce the whole service cost significantly.
3) reclaim carbon dioxide by from the angry body of above-mentioned pair or its burning and gas-exhausting, separating, can improve the thermal efficiency when back segment uses secondary angry body to act as a fuel.Though also depend on the unstrpped gas of use, for instance, under the situation of BFG as unstrpped gas of using steel plant, the thermal efficiency can improve about 2~3 one-tenth.
4) moreover, with above-mentioned secondary angry body (unburned gas) burning and gas-exhausting of gas after using that act as a fuel, the ratio of carbon dioxide is higher, so the further miniaturization of separation reclaimer of carbon dioxide, can improve the emission of carbon-dioxide reduction (separation yield) of steel plant.
According to the 2nd embodiment of the present invention, source and regeneration of absorption solution thermal source take place in the carbon dioxide that is in different places by combination, can effectively and at an easy rate reclaim carbon dioxide from the separation of carbon dioxide generation source.
According to the present invention, can obtain above-mentioned effect simultaneously, thereby can separate the recovery carbon dioxide extremely at an easy rate.So the present invention also is the effective and useful technology that can be used on the industry for the very fierce steel plant of cost competition.
Moreover, according to the present invention, also the carbon dioxide that reclaims for example can be used as reducing gas in the furnace top gas circulation of blast furnace in steel plant.Its result can reduce the consumption of reducing agent, and can reduce the use amount and the CO of coke in blast furnace 2Generating capacity etc., can obviously suppress the rising (according to circumstances, can reduce cost) of the totle drilling cost of steel plant.
In addition, as mentioned above, many technology (comprising the newfound technology of present inventor) that the carbon dioxide that reclaims become valuable product have been proposed also.The present invention has suppressed the rising (because the commodity value of carbon dioxide, the reduction of its totle drilling cost also is possible) of product cost, and a kind of exceedingly useful technology that helps effectively to prevent global warming is provided by the such technology of combination.

Claims (22)

1. one kind is adopted chemical absorption method to separate the method that reclaims carbon dioxide from the secondary angry body that steel plant produce, it is characterized in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, at the described chemical absorbing liquid of heating carbon dioxide is able in the separation processes, utilizes or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
2. one kind is adopted chemical absorption method to separate the method that reclaims carbon dioxide from the burning and gas-exhausting of the secondary angry body of steel plant's generation, it is characterized in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, at the described chemical absorbing liquid of heating carbon dioxide is able in the separation processes, utilizes or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
3. one kind is adopted chemical absorption method to separate the method that reclaims carbon dioxide from the process gas that modifying process produces, wherein modifying process is used for producing hydrogen from the secondary angry body that steel plant produce, described method is characterised in that: with chemical absorbing liquid from this gas behind the absorbing carbon dioxide, make in the technology of carbon dioxide separation at the described chemical absorbing liquid of heating, utilize or apply flexibly 500 ℃ or following low-grade heat extraction that steel plant produce.
4. according to the separation and recovery method of each described carbon dioxide of claim 1~3, it is characterized in that: supply with gas concentration lwevel in the angry body of described pair, burning and gas-exhausting or the process gas of described chemical absorption method and be 15 volume % or more than.
5. according to the separation and recovery method of each described carbon dioxide of claim 1~4, it is characterized in that: the angry body of described pair is at least a kind among blast furnace gas, oven gas and the converter gas.
6. according to the separation and recovery method of each described carbon dioxide of claim 1~5, it is characterized in that: all or part of utilization of the necessary heat of regeneration of described chemical absorbing liquid or apply flexibly the heat extraction that steel plant produce.
7. according to the separation and recovery method of each described carbon dioxide of claim 1~6, it is characterized in that: according to the characteristic of described chemical absorbing liquid, for the multistage utilization of the regeneration of chemical absorbing liquid or apply flexibly the suitable heat extraction that steel plant produce.
8. according to the separation and recovery method of each described carbon dioxide of claim 1~7, it is characterized in that:, use factory's steam simultaneously for the regeneration of described chemical absorbing liquid utilizes or apply flexibly the heat extraction that steel plant produce as much as possible.
9. device that separate to reclaim carbon dioxide from carbon dioxide generation source is characterized in that the formation of this device comprises:
Carbon dioxide absorption equipment, it is used for adopting carbon dioxide absorption medium absorbing carbon dioxide from the gas of being supplied with by carbon dioxide generation source that contains carbon dioxide;
The absorbing medium reclaim equiment, it is used for utilizing absorbing medium regeneration to use the thermal source separating carbon dioxide with the regeneration absorbing medium from the absorbing medium that has absorbed carbon dioxide;
The carbon dioxide absorption medium, its pumped (conveying) medium as carbon dioxide circulates at two equipment rooms; And
Send pipe arrangement and return pipe arrangement, it is used for the transport of carbon dioxide absorbing medium;
Wherein, the absorption equipment of described carbon dioxide is arranged near the carbon dioxide generation source, and described absorbing medium reclaim equiment is arranged on and carbon dioxide generation different place, residing place, source.
10. the separating and reclaiming device of carbon dioxide according to claim 9 is characterized in that: distance A, absorbing medium reclaim equiment between source and the carbon dioxide absorption equipment takes place described carbon dioxide regenerates with absorbing medium and satisfies the relational expression of A<C and B<C with the distance C apart between B and carbon dioxide absorption equipment and the absorbing medium reclaim equiment between the thermal source.
11. the separating and reclaiming device according to claim 9 or 10 described carbon dioxide is characterized in that: be used for the source taking place and supply with sending the pipe arrangement distance Y and returning pipe arrangement apart from Z and be used for from absorbing medium regeneration with thermal source at least one relational expression among the relational expression of the relational expression that satisfies 2X<Y+Z between the pipe arrangement distance W of absorbing medium reclaim equiment heat supply and X+W<Y+Z of the pipe arrangement distance X of the gas that contains carbon dioxide, described carbon dioxide absorption medium to carbon dioxide absorption equipment from described carbon dioxide.
12. the separating and reclaiming device according to each described carbon dioxide of claim 9~11 is characterized in that: described absorbing medium reclaim equiment is arranged on and is used as absorbing medium regeneration with near the technical process heat extraction source of thermal source.
13. the separating and reclaiming device according to each described carbon dioxide of claim 9~12 is characterized in that: utilize the technical process heat extraction as described regeneration of absorption solution part or all with thermal source.
14. the separating and reclaiming device according to each described carbon dioxide of claim 9~13 is characterized in that: the formation of this separating and reclaiming device comprises described 1 cover or overlaps carbon dioxide absorption equipment and 1 cover or overlap regeneration of absorption solution equipment more more.
15. the separating and reclaiming device according to each described carbon dioxide of claim 9~14 is characterized in that: as described regeneration of absorption solution part or all, the multistage technical process heat extraction that utilizes the different temperatures level with thermal source.
16. method of separating the recovery carbon dioxide from carbon dioxide generation source, it is characterized in that: adopt the carbon dioxide absorption equipment that is provided with near carbon dioxide generation source, utilize carbon dioxide absorption medium absorbing carbon dioxide from the gas of supplying with by this carbon dioxide generation source that contains carbon dioxide, utilize regeneration of absorption solution to heat this carbon dioxide absorption medium with thermal source afterwards, employing makes carbon dioxide separation with the regeneration of absorption solution equipment that carbon dioxide generation source is in different places.
17. the separation and recovery method of carbon dioxide according to claim 16 is characterized in that: the distance C apart between B and carbon dioxide absorption equipment and the absorbing medium reclaim equiment between the thermal source of the distance A between described carbon dioxide generation source and the carbon dioxide absorption equipment, absorbing medium reclaim equiment and absorbing medium regeneration usefulness satisfies the relational expression of A<C and B<C.
18. the separation and recovery method according to claim 16 or 17 described carbon dioxide is characterized in that: be used for the source taking place and supply with sending the pipe arrangement distance Y and returning pipe arrangement apart from Z and be used for from absorbing medium regeneration with thermal source at least one relational expression among the relational expression of the relational expression that satisfies 2X<Y+Z between the pipe arrangement distance W of absorbing medium reclaim equiment heat supply and X+W<Y+Z of the pipe arrangement distance X of the gas that contains carbon dioxide, described carbon dioxide absorption medium to carbon dioxide absorption equipment from described carbon dioxide.
19. the separation and recovery method according to each described carbon dioxide of claim 16~18 is characterized in that: described absorbing medium reclaim equiment is arranged on and is used as absorbing medium regeneration with near the technical process heat extraction source of thermal source.
20. the separation and recovery method according to each described carbon dioxide of claim 16~19 is characterized in that: utilize the technical process heat extraction as described regeneration of absorption solution part or all with thermal source.
21. the separation and recovery method according to each described carbon dioxide of claim 16~20 is characterized in that: this separation and recovery method uses described 1 cover or overlaps carbon dioxide absorption equipment and 1 cover or overlap regeneration of absorption solution equipment more more.
22. the separation and recovery method according to each described carbon dioxide of claim 16~21 is characterized in that: as described regeneration of absorption solution part or all, the multistage technical process heat extraction that utilizes the different temperatures level with thermal source.
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