CN103154201B - Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace - Google Patents

Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace Download PDF

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Publication number
CN103154201B
CN103154201B CN201180047923.7A CN201180047923A CN103154201B CN 103154201 B CN103154201 B CN 103154201B CN 201180047923 A CN201180047923 A CN 201180047923A CN 103154201 B CN103154201 B CN 103154201B
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gas
organic substance
volume
waste
transformationreation
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CN103154201A (en
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高木克彦
菅原胜幸
藤井良基
浅沼稔
茂木康弘
斋间等
藤林晃夫
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Treatment Of Sludge (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A method for decomposing an organic substance into lower molecules is provided. In this method, an organic substance is decomposed into lower molecules and converted into gaseous fuel, liquid fuel, or the like. In this process, the organic substance can be efficiently reformed and decomposed into lower molecules using a stable supply of gas to obtain a reformate containing minimal amounts of heavy fractions or carbonaceous materials and large amounts of light fractions. The method can be implemented using relatively simple equipment. An excess of steam is added to an off-gas (g0) that contains carbon monoxide and is generated by a metallurgical furnace, and a shift reaction is performed to obtain a mixed gas (g) containing the hydrogen and carbon dioxide generated by the shift reaction and the steam not consumed by the shift reaction. The mixed gas (g) is brought into contact with the organic substance, and the organic substance is reformed and decomposed into lower molecules. Reforming of the organic substance involves four simultaneously occurring reactions: hydrogenation, hydrogenolysis, steam reforming, and carbon dioxide reforming, allowing decomposition of the organic substance into lower molecules to be facilitated efficiently even at a relatively low reaction temperature.

Description

The waste gas that the degraded method of organic substance and metallurgical furnace produce utilize method
Technical field
The application first invention relates to a kind ofly makes its degraded method by organic substance modification, for the organic substances such as plastic waste are converted to geseous fuel, liquid fuel etc.In addition, the application second invention relates to the method for utilizing of waste gas that a kind of metallurgical furnace produces, the method has been used the degraded method of above-mentioned organic substance, the method is for reducing the burning amount of diffusing (the combustion baked amount of diffusing of the waste gas being produced by metallurgical furnace, combustion diffusion quantity), described waste gas is effectively used in following technique: for making it degraded the organic substance modifications such as plastic waste, be converted to geseous fuel or liquid fuel etc.
Background technology
Now, plastic waste, oil-containing mud, waste oil etc. adopt burning disposal mostly.But, when burning disposal, produce CO 2deng and high to environmental pressure, but also there is the problem of the thermal damage of incinerator, seek to establish chemical reutilization technology.
In chemical reutilization technology, as the technology for organic substance being converted to geseous fuel or liquid fuel, centered by plastic waste, carry out at present various research, and proposed for example following scheme.
A kind of method is disclosed in patent documentation 1, by making, hydrogen concentration 60 volume % are above, preferably the organic substance such as above, the 600 DEG C of above coke-fired furnace gases (COG) of temperature of 80 volume % and plastic waste reacts for it, with high-level efficiency by organic substance hydrocracking, aerification, by the COG gain of heat.
In addition, patent documentation 2 discloses a kind of method, and its catalyzer of holding concurrently the mobile contact catalyst (FCC) of oil as thermal medium uses, and at 350～500 DEG C of temperature, plastic waste is decomposed and is converted to liquid fuel.
In addition, a kind of method is disclosed in patent documentation 3, it is in the time carrying out thermolysis to RDF or timber etc., the gas that thermolysis is generated carries out water vapour upgrading, make to make gas after hydrogen concentration improves in thermolysis portion circulation by this water vapour upgrading, carry out thermolysis having improved in the atmosphere after hydrogen concentration.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-224206 communique
Patent documentation 2: TOHKEMY 2010-013657 communique
Patent documentation 3: TOHKEMY 2001-131560 communique
Patent documentation 4: TOHKEMY 2000-283658 communique
Summary of the invention
The problem that invention will solve
But there is following problem in above-mentioned prior art.
First, about patent documentation 1, hydrogen concentration in COG is more than 60 volume %, even if also only limit to destructive distillation latter stage in dry distillation of coal operation, therefore, in the method for patent documentation 1, need to, at the destructive distillation moment switching gas flow path in latter stage, in plastic waste hydrocarbon hydrocracking reaction device, supply with the more than 600 DEG C COG that contains a large amount of dust.But, under harsh like this condition, be difficult to make flow channel switching valve continuous firing steadily in the long term, from this meaning, can say that this technology lacks realization property.In addition, in order to realize the available gas of plastic waste, need in hydrocarbon hydrocracking reaction device, to supply with the COG that contains the above hydrogen of 60 volume % continuously, for this reason, need to hydrogen concentration meter and flow channel switching valve be all set at each carbonizing chamber, equipment cost increases.
In addition, although the method for patent documentation 2 has promoted catalytic pyrolysis and aromatize by adding FCC catalyzer, but because react under non-active gas flows, therefore heavy oil composition and coke amount to and have generated 13 quality % (embodiment 1), as the manufacturing technology of light Fuel, can not say satisfiable level.
The main body of the gas generating by the method for patent documentation 3 in addition, is H 2, CO, CO 2, it is the slightly low 1800kcal/Nm of waste gas that the combustion heat produces than metallurgical furnace 3the gas of left and right, limited as the value of geseous fuel.
In the prior art for the organic substances such as plastic waste being converted to geseous fuel, liquid fuel, there is problem as above, expect to propose the scheme of the degraded method that relates to organic substance, the degraded method of this organic substance can use can stable supplying gas by organic substance modification and carry out degraded effectively, thereby obtain the modifier that heavy ingredient and carbonaceous are few and contain a large amount of light compositions, and can utilize fairly simple equipment to implement.
On the other hand,, there is at present following problem in effective utilization of the waste gas producing about metallurgical furnace.The various metallurgical furnaces that, batch production is carried out in converter etc. produce a large amount of waste gas off and on producing to synchronize.For example, converter is with instantaneous delivery 10～300,000 Nm 3/ hr left and right produces the waste gas that CO concentration is 50～70 volume % left and right.But, because duration of blast is about 10～30 minutes, be 100,000 Nm at for example instantaneous delivery 3in the situation of/hr, the time average flow including the time of not blowing is 1.7～50,000 Nm 3/ hr left and right.Because low-burning heat is 2000kcal/Nm 3left and right, therefore, converter gas is used effectively as the fuel in iron work etc.But because be intermittently to produce, waste gas must be utilized with the flow below the time average flow in early stage, becomes in fact and the unbalanced state of instantaneous delivery.Therefore, existence cannot be accommodated into the moment of gas-holder completely, and existence must be carried out from flare stack the problem of diffusion combustion.
For such problem, as the using method of the converter gas of the diffusion combustion for suppressing converter gas, following method is disclosed in patent documentation 4: the unit feeding converter gas of synthesis of acetic acid to making the reaction of CO and methyl alcohol, utilizes CO in the converter gas raw material as acetic acid.
But acetic acid is not necessary auxiliary material at iron work, because need to carry out outer selling, in the time lacking the demand of acetic acid, need to reduce its manufacture, existence can not suppress the problem of converter gas purging.
Therefore, the object of the present invention is to provide a kind of degraded method of organic substance, it is by degraded the organic substances such as plastic waste and while being converted to geseous fuel, liquid fuel etc., can use can stable supplying gas by organic substance modification and carry out degraded effectively, thereby obtain the modifier that heavy ingredient and carbonaceous are few and contain a large amount of light compositions, and can utilize fairly simple equipment to implement.
In addition, another object of the present invention is to provide the method for utilizing of waste gas that a kind of metallurgical furnace produces, the method can effectively be utilized the waste gas producing from metallurgical furnace with stable usage quantity, stably reduces the burning amount of diffusing.
The method of dealing with problems
In order to address the above problem, the inventor etc. are studied repeatedly, and result has obtained following opinion.First, in order to solve the first problem, following method is effective: make it carry out transformationreation to adding excessive water vapour in the waste gas that contains carbon monoxide producing in metallurgical furnace, utilization contains the gas after this transformationreation, be the mixed gas of the hydrogen that generates in transformationreation and carbonic acid gas and remaining water vapour, the organic substance modification of high molecular is carried out degraded.In addition we know there is preferred scope in the composition of this organic substance mixed gas (transformationreation generation gas) for modification.
In addition we know, effectively utilize as the unstripped gas that organic substance is carried out to degraded special process as above by waste gas that the metallurgical furnace that contains carbon monoxide is produced, can solve the second problem.; the geseous fuel, the liquid fuel that obtain as the unstripped gas of the degraded technique of specific organism as described above by the gas that the metallurgical furnace that contains carbon monoxide is produced; in the metal melting equipment of iron work etc., be integral; owing to being the fuel being often consumed; so without reducing as required its manufacture; therefore; the gas that metallurgical furnace can be produced stably uses (consumption) as unstripped gas; so, can stably reduce the burning of gas amount of diffusing that metallurgical furnace produces.
The present invention completes based on above-mentioned opinion, and its purport is as follows.
[1] a degraded method for organic substance, the method comprises: by the waste gas (g that contains carbon monoxide producing in metallurgical furnace 0) in add excessive water vapour make it carry out transformationreation, the mixed gas (g) of water vapour that formation contains hydrogen that transformationreation generates and carbonic acid gas and do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, organic substance modification is carried out degraded.
[2] the degraded method of the organic substance described in above-mentioned [1], wherein, waste gas (g 0) be, in the waste gas that contains carbon monoxide and nitrogen by producing from metallurgical furnace, at least a portion nitrogen is separated to the waste gas that has improved carbon monoxide concentration.
[3] the degraded method of the organic substance described in above-mentioned [1] or [2], wherein, the water vapor concentration of mixed gas (g) is 5～70 volume %.
[4] the degraded method of the organic substance described in above-mentioned [3], wherein, in mixed gas (g), water vapor concentration is that 20～70 volume %, hydrogen concentration are that 10～40 volume %, gas concentration lwevel are 10～40 volume %.
[5] the degraded method of the organic substance described in any one in above-mentioned [1]～[4], wherein, the organic substance for the treatment of modification is to be selected from more than one in plastic waste, oil-containing mud, waste oil.
[6] manufacture method for fuel, the method comprises: the modifier of the organic substance that the degraded method of the organic substance by described in any one in above-mentioned [1]～[5] is obtained reclaims with the form of geseous fuel and/or liquid fuel.
[7] waste gas that metallurgical furnace produces utilize a method, the method comprises: the waste gas (g that contains carbon monoxide that has temporary transient storage and produce off and on from metallurgical furnace 0) gas-holder, will be stored in the waste gas (g of this gas-holder 0) deliver to gas and utilize the pipe arrangement and can not be stored in the waste gas (g of gas-holder of supplying gas of equipment 0) carry out in the exhaust gas apparatus of flare stack of diffusion combustion, by the pipe arrangement combustion gas (g that supplies gas from the described pipe arrangement branch of supplying gas 0) a part, to this waste gas (g 0) in add excessive water vapour make it carry out transformationreation, the mixed gas (g) of water vapour that formation contains hydrogen that transformationreation generates and carbonic acid gas and do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, organic substance modification is carried out degraded.
[8] above-mentioned [7] described method, wherein, adds excessive water vapour and makes it carry out the waste gas (g of transformationreation 0) be, the waste gas that contains carbon monoxide and nitrogen by producing from metallurgical furnace, at least a portion nitrogen is separated to the waste gas that has improved carbon monoxide concentration.
[9] the described method in above-mentioned [7] or [8], wherein, the water vapor concentration of mixed gas (g) is 5～70 volume %.
[10] above-mentioned [9] described method, wherein, in mixed gas (g), water vapor concentration is that 20～70 volume %, hydrogen concentration are that 10～40 volume %, gas concentration lwevel are 10～40 volume %.
[11] method described in any one in above-mentioned [7]～[10], wherein, the organic substance for the treatment of modification is to be selected from more than one in plastic waste, oil-containing mud, waste oil.
[12] manufacture method for fuel, the method comprises: the modifier of the organic substance obtaining by the method described in any one in above-mentioned [7]～[11] is reclaimed with the form of geseous fuel and/or liquid fuel.
The effect of invention
Invent according to the application first, by degraded the organic substance of the high molecular such as plastic waste and while being converted to geseous fuel, liquid fuel etc., can use can stable supplying gas organic substance is high effective and modified and carry out degradedly, obtain the high calorie modifier that heavy ingredient or carbonaceous are few and contain a large amount of light compositions.In addition, about facilities and equipments, do not need special gauger or flow channel switching valve etc. yet, even and under lower temperature of reaction, also can carry out the modification of organic substance, therefore, can utilize fairly simple equipment to implement.In addition, the CO generating by transformationreation 2because be converted into CO by carbonic acid gas upgrading reaction in the modification of organic substance, therefore, can implement the chemistry recycling of organic substance and do not increase CO 2generation.
In addition, invent according to the application second, the waste gas producing effectively can be utilized as unstripped gas degraded to organic substances such as plastic waste and that be converted to the special process of geseous fuel, liquid fuel etc. as the metallurgical furnace that contains carbon monoxide of the lower waste gas of heat.Geseous fuel, liquid fuel are indispensable in the metal melting equipment of iron work etc., stablized the fuel of consumption, thereby without reducing as required manufacture, therefore, the waste gas that metallurgical furnace can be produced stably uses (consumption) as unstripped gas, thus, can also make the burning amount of diffusing of the waste gas of metallurgical furnace generation stably reduce.Particularly in the metal melting equipment of iron work etc., fuel consumption, turnout in generation and the equipment of the waste gas that metallurgical furnace produces are proportional, the generation of the waste gas that therefore metallurgical furnace produces is also proportional with the usage quantity of the waste gas that the metallurgical furnace for fuel making produces, from this side considerations, also can make the burning amount of diffusing of the waste gas of metallurgical furnace generation stably reduce.
In addition, from the processing aspect of the organic substances such as plastic waste, by degraded the organic substance of the high molecular such as plastic waste and while being converted to geseous fuel, liquid fuel etc., can use can stable supplying the waste gas that produces of metallurgical furnace effectively modification organic substance and carry out degraded, thereby obtain heavy ingredient and carbonaceous is few and the high calorie modifier that contains a large amount of light compositions.In addition, about facilities and equipments, do not need special gauger or flow channel switching valve etc. yet, even and under lower temperature of reaction, also can carry out the modification of organic substance, therefore, can utilize fairly simple equipment to implement.In addition, the CO generating by transformationreation 2can be in the time of the modification of organic substance in the reaction of carbonic acid gas upgrading, be changed to CO, therefore, can implement the chemistry recycling of organic substance and do not make CO 2generation increases.
Brief description of the drawings
[Fig. 1] is the graphic representation being illustrated in to the relation between the gas composition after addition and the transformationreation of water vapour in the transformationreation of adding water vapour in converter gas and carry out (temperature 430 DEG C at equilibrium composition calculated value);
[Fig. 2] is the structure iron that the exhaust gas apparatus of the converter of existing general iron work is shown;
[Fig. 3] is the structure iron that an embodiment for implementing equipment of the present invention is shown;
[Fig. 4] illustrates that transformationreation in embodiment 1 generates the graphic representation of the vaporization rate in water vapor concentration and the poly modification (degraded) of gas and the relation between liquefied fraction;
[Fig. 5] illustrates that transformationreation in embodiment 1 generates the graphic representation of the relation between the water vapor concentration of gas and the LHV of the geseous fuel obtaining by poly modification (degraded) and liquid fuel;
[Fig. 6] illustrates that transformationreation in embodiment 1 generates the graphic representation of the relation between the polyethylene decomposition rate in water vapor concentration and the poly modification (degraded) of gas;
[Fig. 7] be illustrate that transformationreation in embodiment 1 generates the gas concentration lwevel of gas and the hydrogen concentration of the geseous fuel that obtains by poly modification (degraded) between the graphic representation of relation;
[Fig. 8] be illustrate that transformationreation in embodiment 1 generates the hydrogen concentration of gas and the gas concentration lwevel of the geseous fuel that obtains by poly modification (degraded) between the graphic representation of relation;
[Fig. 9] is the explanatory view of the equipment that uses in schematically illustrated embodiment 1 (example 11);
[Figure 10] is the graphic representation that the passing of the gas-holder level in conventional example and the amount of diffusing of burning is shown;
[Figure 11] is the graphic representation that gas-holder level in the example of embodiment 2 and the passing of the burning amount of diffusing are shown;
[Figure 12] is the graphic representation that the accumulative total burning amount of diffusing of the conventional example obtained by Figure 10 and Figure 11 and the inventive example is shown.
Nomenclature
1 converter
2 gas recovery units
3 T-valve
4 flare stacks
5 gas-holder
6 pipe arrangements of supplying gas
7 gases utilize equipment
8 shift-converters
9 modified-reaction devices
10 liquid fuel traps
11 gas coolers
60 pipe arrangements of supplying gas
90 gas dispersion plates
A treatment facility
A polyethylene
B net
C Ni catalyzer
Embodiment
The degraded method of the organic substance of first, the application first being invented describes.
Method of the present invention is by the waste gas (g that contains carbon monoxide producing to metallurgical furnace 0) (following, be sometimes referred to as " metallurgical furnace produce waste gas ") add excessive water vapour and make it carry out transformationreation, the mixed gas (g) of the water vapour not consuming in the hydrogen that formation contains transformationreation generation and carbonic acid gas and transformationreation, make this mixed gas (g) (following, be sometimes referred to as " transformationreation generation gas ") contact with organic substance, organic substance modification is carried out degraded.It should be noted that, to waste gas (g 0) in add excessive water vapour refer to that the mode that do not remain in mixed gas (g) of remaining water vapour not consume adds water vapour in transformationreation.
For such method of the present invention, even if also can effectively promote the degraded of organic substance under lower temperature of reaction, hydrogen consumption is also few, and the almost generation to heavy ingredient and carbonaceous unconfirmed.
When the contour molecular weight organic material of known plastic waste heats more than 300～400 DEG C, conventionally can start thermolysis, now, carrying out lighting simultaneously, also can carry out heaviness.If hydrogen is coexisted in the time of thermolysis, carry out hydrogenation reaction and hydrocarbon hydrocracking reaction to hydrocarbon kind, therefore, for suppress heaviness and degraded be effective.But, exist hydrocracking to need high temperature, and the problem that increases of hydrogen consumption.
On the other hand, water vapour upgrading, carbonic acid gas upgrading can be regarded as H 2o, CO 2the oxidation of the hydrocarbon that the oxygen in molecule causes, can realize generation degraded and inhibition carbonaceous with few hydrogen addition.And water vapour upgrading and carbonic acid gas upgrading have the feature that temperature of reaction reduces along with the carbon chain growth of the organic molecule being modified.In method of the present invention, even if also can effectively promote the degraded of organic substance under lower temperature of reaction, hydrogen consumption is also few, and the almost generation to heavy ingredient and carbonaceous unconfirmed, this can think owing to being carried out the modification (degraded) of organic substance and being carried out hydrogenation, hydrocracking, water vapour upgrading, these four reactions of carbonic acid gas upgrading by the above-mentioned mixed gas of use (g) simultaneously.
For example, the waste gas producing from metallurgical furnaces such as converters, conventionally contain the CO of 25～80 volume % left and right.Therefore,, if add wherein water vapour, generate H by following transformationreation (1) 2and CO 2.
CO＋H 2O→H 2＋CO 2…(1)
In method of the present invention, due to waste gas (g 0) the excessive water vapour of middle interpolation, therefore, in the mixed gas (g) after transformationreation, comprise the H generating by transformationreation 2, CO 2h with excessive interpolation 2o.And can think, in the modification (degraded) of the organic substance that utilizes this transformationreation generation gas (g) to carry out, carry out hydrogenation, hydrocracking, water vapour upgrading, these four reactions of carbonic acid gas upgrading of each gaseous constituent simultaneously.
In the present invention, can be by the excessive waste gas (g that adds to of suitable control 0) in the extra proportion of water vapour and the reactivity of transformationreation control each concentration of water vapour in gas, hydrogen, carbonic acid gas, thereby form organic mixed gas (g) for substance modification.But, for example, be generally CO:50～70 volume %, CO because be stored in the composition of the waste gas of the metallurgical furnace generation in gas-holder (the common gas-holder, using) in iron work 2: 10～20 volume %, N 2: 10～20 volume %, H 2: 0～5 volume % (containing in addition saturated steam) left and right, therefore, the general reactivity control that does not need to carry out transformationreation, can only be controlled at desired level by the extra proportion of adjusting water vapour by each concentration of the water vapour in mixed gas (g), hydrogen, carbonic acid gas.
It should be noted that, the reactivity of transformationreation can be controlled by the residence time being adjusted in shift-converter.For example, in order to shorten the residence time, conventionally adopt the method that reduces shift-converter length or reduce catalyzer loading level, in this situation, shift-converter length and catalyzer loading level can be set as reaction and proceed to 1/2～1/4 left and right while reaching in a basic balance.
As an example, for comprising CO:65 volume %, CO 2: 15 volume %, N 2: 18 volume %, H 2: 1 volume %, H 2converter gas the 100kmol/h (=2240Nm of the composition of O:1 volume % 3/ make the addition of water vapour from 60kmol/h (=1340Nm in h) 3/ h) be changed to 540kmol/h (=12100Nm 3/ h) carrying out the situation of transformationreation, Fig. 1 illustrates gas composition after water vapour addition and transformationreation (temperature 430 DEG C at equilibrium composition calculated value).Hence one can see that, can control by only adjusting water vapour addition each concentration of water vapour in mixed gas (g), hydrogen, carbonic acid gas, and become preferred gas composition as hereinafter described.In addition we know, transformationreation is conventionally performed until to react and reaches in a basic balance.
Below, the details to method of the present invention and preferred condition describe.
In the present invention, as the waste gas (g that carries out transformationreation 0) the reasons are as follows of waste gas that use metallurgical furnace to produce: the waste gas that metallurgical furnace produces contains carbon monoxide with higher concentration, and the concentration of unwanted nitrogen is low.Waste gas (the g producing as the metallurgical furnace that contains carbon monoxide 0), can use waste gas arbitrarily.The most representative be by carry out iron and steel manufacturing process decarbonization process converter produce converter gas, in addition, for example can enumerate the waste gas of generation from change iron preprocessing furnace, fusion reducing furnace, shaft furnace etc., can use one or more the mixed gas in these waste gas.
The carbon monoxide that generates in metallurgical technology is further oxidized and generate the ratio of carbonic acid gas, i.e. post-combustion rate (CO 2/ (CO+CO 2) × 100) be conventionally only 10～50% left and right.In addition, at waste gas (g 0) in also contain hydrogen and nitrogen, H 2concentration changes according to metallurgical technology, is 0～20 volume % left and right.Nitrogen is supplied with for stirring and flue protection etc. in stove, and it is at waste gas (g 0) in concentration be generally 10～30 about volume %.
According to above aspect, the waste gas (g that general metallurgical furnace produces 0) composition be roughly following scope.
CO:80～25 volume % (being equivalent to post-combustion rate 10～50%)
CO 2: 10～25 volume % (being equivalent to post-combustion rate 10～50%)
N 2: 10～30 volume %
H 2: 0～20 volume %
Transformationreation needs carbon monoxide, needs only the composition of gas in above-mentioned scope, waste gas (g 0) composition there is no special problem.Here, nitrogen can not bring any contribution to the chemical reaction occurring in the present invention (transformationreation, hydrogenation, hydrocracking, water vapour upgrading, carbonic acid gas upgrading), on the other hand, geseous fuel to manufacturing dilutes, low-burning heat (following, to be called " LHV ") is reduced.Particularly, if nitrogen concentration exceedes 50 volume %, the LHV of geseous fuel significantly reduces, and transformationreation speed also exists the tendency of reduction.Therefore, nitrogen concentration is preferably in above-mentioned compositing range.
As narrated above, the composition that is stored in the waste gas of the metallurgical furnace generation of gas-holder (the general gas-holder for example, using) in iron work is generally CO:50～70 volume %, CO 2: 10～20 volume %, N 2: 10～20 volume %, H 2: 0～5 volume % (in addition, comprising saturated steam) left and right, is equivalent to high CO concentration composition in the composition of the waste gas that this composition produces at above-mentioned general metallurgical furnace.Be stored in gas in gas-holder because the each factory in iron work is used as fuel gas, therefore, need to prevent from utilizing the reduction of efficiency of combustion in place.Therefore the reason that, the lower value of CO concentration in gas is set as to the storage requirement in gas-holder is because formed high CO concentration composition.
In the present invention, be no matter the composition of the waste gas that produces of being stored in of using in the iron work waste gas that CO concentration such in common gas-holder is higher or common metallurgical furnace as above, can serve as waste gas (g 0) be used.
But, the waste gas (g producing at metallurgical furnace 0) in, exist as installation for blast furnace gas etc. the gas that carbon monoxide concentration is lower and nitrogen concentration is high, for the waste gas (g of such metallurgical furnace generation 0), can be at least a portion of the nitrogen containing being separated to (removing) after having improved carbon monoxide concentration, then add excessive water vapour and make it carry out transformationreation.In addition, because the nitrogen concentration in waste gas depends on the standard that requires at the combustion heat of the geseous fuel of the degraded middle generation of organic substance, can not unify to determine, if but nitrogen concentration in waste gas exceedes 30 volume %, nitrogen separation circuit is preferably set in order to from waste gas (g 0) middle (removing) at least a portion nitrogen that separates.
As the representational waste gas that preferably carries out nitrogen separation, can enumerate installation for blast furnace gas, in addition, can also enumerate electric furnace or the condition that increases at nitrogen concentration under the waste gas that produces of the shaft furnace of operation etc.In addition, also can carry out nitrogen separation for the waste gas that contains higher concentration carbon monoxide as converter gas etc., further improve after carbon monoxide concentration, then carry out transformationreation.
Method for separating nitrogen from waste gas is not particularly limited, and can use the method arbitrarily such as adsorption method of separation, distillation and separation method, but because the boiling-point difference of nitrogen and carbon monoxide is less, therefore adsorption method of separation particularly preferably.For example,, due to as CO sorbent material and known load has Cu +also CO absorption of gac 2, therefore can be by having Cu with load +gac as the PSA method of sorbent material, (roughly formed: N by installation for blast furnace gas 2: 50 volume %, CO:25 volume %, CO 2: 25 volume %) obtain roughly consisting of N as desorption gas 2: 15 volume %, CO:45 volume %, CO 2: the gas of 40 volume %, this gas is by the nitrogen separation in installation for blast furnace gas and the gas after making carbon monoxide concentrated.
Transformationreation in method of the present invention is not particularly limited, and can adopt known method.In general waste gas (the g, producing to metallurgical furnace in advance 0) in add water vapour, and imported to and in the fixed-bed reactor of having filled catalyzer, carried out transformationreation.In addition, also can add in advance part water vapour, and in reactor, add catalyzer by the multistage, then add remaining water vapour between catalyst layer and catalyst layer.
In addition, if the waste gas (g producing to metallurgical furnace respectively 0) in add water vapour, hydrogen, carbonic acid gas and do not carry out transformationreation as the present invention, also can obtain the gas with the organic substance obtaining mixed gas (g) same composition for modification in transformationreation of the present invention, but in such method, except water vapour, also must add hydrogen and the carbonic acid gas of high price, cost increases.
In the present invention, the organic substance being obtained by transformationreation for modification mixed gas (g) comprise water vapour, hydrogen and carbonic acid gas, their concentration is not particularly limited, but due to following reason, preferably water vapor concentration is 5～70 volume %.; if water vapor concentration is low; the rate of decomposition of the organic substance such as plastic waste reduces; more than water vapor concentration being set as to 5 volume %; can guarantee the rate of decomposition of the organic substance of certain level; can make the production rate (vaporization rate) of geseous fuel, the production rate (liquefied fraction) of liquid fuel is certain level, can reduce the growing amount of heavy ingredient.On the other hand, if water vapor concentration is high, in generating gas (gas of the degraded generation of the modification by organic substance, lower with), the modified-reaction of organic substance is easy to residual CO 2, and the LHV of geseous fuel, liquid fuel easily reduces, if water vapor concentration is below 70 volume %, can suppresses modified-reaction and generate the CO in gas 2residual, in addition, can also suppress geseous fuel, liquid fuel LHV reduce.
In addition, from guarantee organic substance rate of decomposition viewpoint consider, more than the hydrogen concentration in mixed gas (g) and gas concentration lwevel are all preferably 5 volume %.
In addition, due to following reason, the preferred water vapor concentration that consists of of organic substance mixed gas (g) for modification: 20～70 volume %, hydrogen concentration: 10～40 volume %, gas concentration lwevel: 10～40 volume %.It should be noted that, in this mixed gas (g), also can contain other gaseous constituent (such as nitrogen etc.).More than water vapor concentration being made as to 20 volume %, can fully improving the rate of decomposition of organic substance, and can improve the LHV of geseous fuel.Water vapor concentration is made as to reason below 70 volume % as narrated above.By hydrogen concentration being made as to 10 volume % above (more preferably more than 12 volume %), particularly, in the case of than carrying out under lower temperature the modified-reaction of organic substance, also can be suppressed at residual CO in geseous fuel 2.By gas concentration lwevel being made as to 10 volume % above (more preferably more than 13 volume %), in geseous fuel, be difficult for residual heat than hydrocarbon and the low gaseous constituent H of CO 2.In addition, by hydrogen concentration, gas concentration lwevel are made as below 40 volume %, the rate of decomposition that can make the organic substances such as plastic waste is preferred level.In addition, according to above viewpoint, the preferred gas composition of mixed gas (g) is water vapor concentration: 25～65 volume %, hydrogen concentration: 15～35 volume %, gas concentration lwevel: 15～35 volume %.In addition, in this mixed gas (g), also can contain other gaseous constituent (such as nitrogen etc.).
In addition, as one of feature of the present invention, can enumerate and can control geseous fuel growing amount in the modification of organic substance and the ratio of liquid fuel growing amount by the water vapor concentration of organic substance mixed gas (g) for modification.; if more than the water vapor concentration of mixed gas (g) is set as to 50 volume %; mainly generate geseous fuel (; geseous fuel growing amount > liquid fuel growing amount); if water vapor concentration is made as below 40 volume %; mainly generate liquid fuel (, geseous fuel growing amount < liquid fuel growing amount).It should be noted that, the impact of hydrogen concentration, gas concentration lwevel is so remarkable not as the impact of water vapor concentration, therefore needs only in preferable range of the present invention.
Below, the condition that the mixed gas (g) employing transformationreation being obtained carries out the modification (degraded) of organic substance describes.
In the present invention, as the organic substance of the object degraded by modification, be not particularly limited, but the preferred organic substance of high molecular for example, can be enumerated plastic waste, oil-containing mud, waste oil etc., can be taking more than one in them as object.
Here, oil-containing mud refers to the mixture of the sludge-like producing in oily waste liquor treatment process, generally contains the moisture of 30～70 quality % left and right.As the oil content in mud, can enumerate such as various mineral oil, natural and/or synthetic oil lipid, various fatty acid esters etc., but be not limited to these.In addition, in order to improve to modified-reaction device (for organic substance modification is made to its degraded reactor, lower with) operability while supplying with oil-containing mud etc., also can make the moisture in mud be reduced to 30～50 quality % left and right by methods such as centrifugations.
In addition, as waste oil, can enumerate the various mineral oil that for example use, natural and/or synthetic oil lipid, various fatty acid esters etc., but be not limited to these.In addition, can be also the two or more mixture in above-mentioned waste oil.In addition, in the rolling process of iron work, produce waste oil time, generally contain the moisture of a large amount of (are generally and exceed 80 quality % left and right), from operability aspect, it is favourable by methods such as proportion separation, this moisture being reduced in advance.
In the situation that organic substance contains water, owing to producing water vapour in modified-reaction device, therefore, consider that the water vapour of this part decides the extra proportion of the water vapour adding in transformationreation.
In addition, if plastic waste contains the chlorine-containing resins such as polyvinyl chloride, in modified-reaction device, produce chlorine, this chlorine may be included in geseous fuel, liquid fuel.Therefore, in the situation that plastic waste may contain chlorine-containing resins, preferably to drop in modified-reaction device as CaO etc. chlorine absorption agent so that chlorine-containing component not in the geseous fuel of generation, liquid fuel.
Temperature of reaction when preferred organic substance modification is set as follows according to the kind of organic substance.The in the situation that of plastic waste, temperature of reaction is that 400～900 DEG C of left and right are more suitable.Temperature of reaction is during lower than 400 DEG C, and the rate of decomposition of plastic waste is low, and on the other hand, if temperature of reaction exceedes 900 DEG C, the generation of carbonaceous increases.In addition, under oil-containing mud or useless oil condition, temperature of reaction is that 300～800 DEG C of left and right are more suitable.In temperature of reaction, during lower than 300 DEG C, the rate of decomposition of oil-containing mud or waste oil reduces.On the other hand, temperature of reaction exceedes 800 DEG C, and modification (degraded) characteristic on oil-containing mud or waste oil is without impact, but because be required above high temperature, uneconomical.In addition, at the mixture taking plastic waste and oil-containing mud and/or waste oil, as object, from the point of view, temperature of reaction is that 400～800 DEG C of left and right are more suitable.In addition, temperature of reaction does not affect substantially on the ratio of geseous fuel growing amount and liquid fuel growing amount.In addition, also substantially unconfirmed to the impact of pressure on it, therefore, make modified-reaction device at normal pressure or a few kg/cm 2micro-the adding of left and right, is depressed comparatively economy of running.
The kind of modified-reaction device is not particularly limited, move smoothly in reactor from organic substances such as plastic waste, and can with organic substance for modification mixed gas (g) effectively contact aspect consider, the preferably Horizontal mobile hearth reactor as rotary kiln.
In addition, in the present invention, in the modification of organic substance, do not need especially catalyzer, but can react by catalyst filling yet.As catalyzer, can use there is respectively water vapour upgrading activity, one or more catalyzer of carbonic acid gas upgrading activity, hydrogenation activity, hydrocracking activity.As concrete example, can enumerate Ni is that modified catalyst, Ni are hydrogenation catalyst, Pt/ zeolite through-stone oil refining catalyzer etc.In addition, the dust that known packets produces containing the converter of fine Fe particle also can be used as modified catalyst or hydrocracking catalyst.
The in the situation that of catalyst filling, good with contacting of catalyzer from the viewpoint of organic substances such as plastic waste, can adopt vertical so horizontal moving-bed type modified-reaction device such as modified-reaction device instead of rotary kiln.In this situation, the mixed gas (g) obtaining in transformationreation, moving-bed type modified-reaction device.In this situation, compared with the situation of supplying with the mixed gas (g) obtaining from the top of modified-reaction device transformationreation, from bottom and/or when sidepiece supplies with the mixed gas (g) obtaining transformationreation, mixed gas (g) is better with contacting of organic substance or catalyzer, therefore preferably.
As vertical modified-reaction device, can use the common fixed-bed reactor that use in chemical industry, particularly, in the case of adopting from the mode of modified-reaction device underfeed mixed gas (g), can be used as blast furnace, shaft furnace or the converter of ironmaking equipment as modified-reaction device.Using blast furnace, shaft furnace use as modified-reaction device in the situation that, if be made into following moving-bed type, reaction efficiency increases, thereby preferably, described moving-bed type is: supply with continuously organic substance and catalyzer from stove top, from stove underfeed mixed gas (g), make their convection current contacts, and continuously from stove top withdrawing gas resultant, extract liquid resultant and catalyzer out from stove bottom.In addition, in the situation that using converter as modified-reaction device, the intermittent reaction form that can make and blow identical,, after in organic substance and catalyzer are put into stove, supply with continuously mixed gas (g) from stove bottom, the withdrawing gas resultant continuously from stove top, liquid resultant and catalyzer tilt stove and extract out after the reaction of certain hour.
The modifier of the organic substance that method of the present invention obtains is generally gas and liquid, and they are suitable to geseous fuel, liquid fuel.
Combustiblecomponents in geseous fuel is made up of the hydrocarbon of carbon monoxide and C1～C4, and its LHV is about 6～10Mcal/Nm 3.So, it has following feature: although its LHV and Sweet natural gas are equal to, because carbon monoxide concentration is high, compared with natural-gas, its incendivity is high.Because carbon monoxide concentration is high and incendivity is high, from the viewpoint of security, be compared to mutually home-use city gas and supply with, more preferably utilize as the city gas instead fuel of the factory with metallurgical furnace as iron work etc.
Liquid fuel is made up of the hydrocarbon of C5～C24, therefore be the mixture of petroleum naphtha (C5～C8), lam-oil (C9～C12), light oil (C13～C24), for substantially not containing the lightweight oil of the high-quality that is equivalent to heavy oil (more than C25).This liquid fuel also can be made respectively petroleum naphtha, lam-oil, light oil by fractionation by distillation and use, and uses but also can be using the form of mixture as iron work etc. such fuel of the factory with metallurgical furnace or the heavy oil of ore hearth substitute reductive agent.
It should be noted that, because the containing ratio of petroleum naphtha (C5～C8) is many, except using as light liquid fuel, also can will after petroleum naphtha composition fractionation by distillation, use as chemical industry raw material.To this, can enumerate the method for utilizing of the petroleum naphtha composition after fractionation by distillation being carried out to catalytic modification and be converted to benzene,toluene,xylene etc.
Utilize the modifier of the organic substance that method of the present invention obtains modified-reaction can generated after gas cooling, be separated into respectively geseous fuel and liquid fuel by gas-liquid separation.In addition, can from liquid fuel, isolate as required petroleum naphtha, lam-oil, light oil by fractionation by distillation.Method of cooling, gas-liquid separating method and distillation separation method that modified-reaction generates gas can be undertaken by known method, are not particularly limited.
In addition, from the viewpoint of the above, as long as use the mixed gas of mixed gas (g) same composition obtaining with the present invention, just decomposing organic matter matter and make it degraded effectively.Particularly by using water vapor concentration: 20～70 volume %, hydrogen concentration: 10～40 volume %, gas concentration lwevel: 10～40 volume %, more preferably use water vapor concentration: 25～65 volume %, hydrogen concentration: 15～35 volume %, gas concentration lwevel: the mixed gas of 15～35 volume %, the rate of decomposition of organic substance can be fully improved, and the LHV of geseous fuel can be improved.It should be noted that, in this mixed gas, also can contain other gaseous constituent (such as nitrogen etc.).
Limit the reason of such gas composition identical with the restriction reason of the invention described above method.In order to utilize method beyond method of the present invention to obtain the mixed gas of above-mentioned composition, for example, need in basic gas, add more than one in water vapour, hydrogen, carbonic acid gas.
The condition of modification (degraded) of organic substance of utilizing this mixed gas to carry out is identical with the condition of the modification (degraded) of the invention described above method.
Therefore, the purport of the method is as following [i]～[iv], the embodiment that aftermentioned " embodiment 1 " of the present invention is also the method for following [i]～[iv].
The degraded method of [i] a kind of organic substance, it is characterized in that, making water vapor concentration is that 20～70 volume %, hydrogen concentration are that 10～40 volume %, gas concentration lwevel are that the mixed gas of 10～40 volume % contacts with organic substance, and organic substance modification is carried out degraded.
The degraded method of [ii] a kind of organic substance, is characterized in that, in the method for above-mentioned [i], the water vapor concentration of mixed gas is that 25～65 volume %, hydrogen concentration are that 15～35 volume %, gas concentration lwevel are 15～35 volume %.
The degraded method of [iii] a kind of organic substance, is characterized in that, in the method for above-mentioned [i] or [ii], the organic substance for the treatment of modification is to be selected from more than one in plastic waste, oil-containing mud, waste oil.
The manufacture method of [iv] a kind of fuel, is characterized in that, the modifier of the organic substance obtaining by any method in above-mentioned [i]～[iii] is reclaimed with the form of geseous fuel and/or liquid fuel.
The method of utilizing of the waste gas that the metallurgical furnace of below, the application second being invented produces describes.
Various metallurgical furnaces a large amount of waste gas of intermittent generation in producing of batch production is carried out in converters etc.For example, converter is taking instantaneous delivery as 10～300,000 Nm 3/ hr left and right produces the waste gas that CO concentration is 30～70 volume % left and right.But, because duration of blast is about 10～30 minutes, therefore, to comprise the time of not blowing at interior time average under meter, be only 1.7～50,000 Nm 3/ hr (instantaneous delivery 100,000 Nm 3in the situation of/hr), there is larger difference with instantaneous delivery.Because the low-burning heat of converter gas is 1800～2000kcal/Nm 3left and right, therefore can be used as fuel in iron work etc. and is used effectively.But because be intermittently to produce, waste gas must be with the flow utilization below the time average flow in early stage, become in fact and the unbalanced state of instantaneous delivery.Therefore, there is following problem: existence can not be accommodated into the moment of gas-holder completely, must carry out diffusion combustion from flare stack.
Shown in Fig. 2 is the exhaust gas apparatus of the converter in general iron work.Reclaimed by gas recovery unit 2 from converter 1 expellant gas, by gas-holder 5 (for example, what Wei Jinsi (Wiggins) formula gas-holder was such possess in inside movable piston forms and the gas-holder of volume-variable) as snubber, by supplying gas, pipe arrangement 6 utilizes equipment 7 to supply gas to the each gas in iron work.Now, because the larger difference of above-mentioned time average flow and instantaneous delivery, generation can not be accommodated into the situation of gas-holder 5 completely, therefore, T-valve 3 is switched to flare stack 4 sides, and waste gas is carried out to diffusion combustion.Particularly, in the case of the blowing of another not shown converter is overlapping, owing to forming very large instantaneous delivery, therefore become the state that can not avoid diffusion combustion.
In order to reduce the burning amount of diffusing, as mentioned above, increase exhaust gas utilization amount in iron work comparatively effective, but iron work at home is particularly difficult to utilize to heavens waste gas, thereby merely increases utilization.
But in order to blow into blast furnace and the gain of heat to oneself the generating field fuel gas using ironmaking waste gas as fuel etc., the such high calorie fuel of Sweet natural gas and oil is used as auxiliary fuel or auxiliary carbon material uses.Therefore, if waste gas can be converted to high calorie fuel, can have a net increase of exhaust gas utilization amount, its result, can reduce the burning amount of diffusing.
Therefore, in the present invention, in gas recovery unit, by by the pipe arrangement combustion gas (g that supplies gas by the above-mentioned pipe arrangement branch of supplying gas 0) a part, and set it as and the organic substances such as plastic waste are carried out to unstripped gas degraded and that be converted to the above-mentioned special process (the degraded method of the organic substance that the application who narrates first invents) of geseous fuel, liquid fuel etc. above use, described gas recovery unit has: temporarily store as above from the intermittent waste gas (g that contains carbon monoxide producing of metallurgical furnace 0) (following, to be sometimes referred to as " waste gas that metallurgical furnace produces ") gas-holder, will be stored in the waste gas (g of this gas-holder 0) be transported to the pipe arrangement of supplying gas that gas utilizes equipment, flare stack that the waste gas (g0) that can not be stored in gas-holder carries out diffusion combustion., by waste gas (g 0) in add excessive water vapour make it carry out transformationreation, the mixed gas (g) of water vapour that formation contains hydrogen that transformationreation generates and carbonic acid gas and do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, organic substance modification is carried out degraded.
Like this, the present invention using metallurgical furnace produce waste gas as the organic substances such as plastic waste are carried out degraded and be converted to geseous fuel, liquid fuel etc. special process unstripped gas use.Geseous fuel, liquid fuel are indispensable in the metal melting equipment of iron work etc., it is stably consumed, therefore without reducing as required its manufacture, therefore, the waste gas that metallurgical furnace can be produced stably uses (consumption) as unstripped gas, thus, can also stably reduce the burning amount of diffusing of the waste gas of metallurgical furnace generation.
It should be noted that, the feature of the degraded processing of the organic substance carrying out in the present invention and advantage are described in the degraded method of the organic substance of inventing in the application first above.
Fig. 3 is the pie graph of an embodiment for implementing equipment of the present invention, and shown in it is that the waste gas that metallurgical furnace produces is the situation of converter gas.In figure, A is treatment facility, and it is with waste gas (g 0) for unstripped gas, carry out degraded organic substance and be converted to the processing of geseous fuel and liquid fuel, the 8th, form the shift-converter of this treatment facility A, 9 are similarly modified-reaction device.
With Fig. 2 similarly, the waste gas (g discharging from converter 1 0) reclaimed by gas recovery unit 2, using gas-holder 5 as snubber, utilize equipment 7 to supply gas by the pipe arrangement 6 of supplying gas to the each gas in iron work, discharge the waste gas (g of requirement by the pipe arrangement 60 of supplying gas of the branch midway from the pipe arrangement 6 of supplying gas 0), and set it as for unstripped gas degraded organic substance and that be converted to geseous fuel/liquid fuel is delivered to treatment facility A.
For treatment facility A, to waste gas (g 0) in after mixed vapour (as described later, the mixing of this steam also can be carried out a part in shift-converter 8), imported shift-converter 8 and carried out transformationreation, then the mixed gas after this transformationreation (g) (transformationreation generation gas) is imported to the modification (degraded) of carrying out organic substance in modified-reaction device 9.
In addition, the details of the degraded processing of the organic substance of method of the present invention and preferred condition, as described in the degraded method of the organic substance of inventing as the application first above.Therefore waste gas (the g that, utilizes metallurgical furnace to produce 0), can improve carbon monoxide concentration by least a portion of contained nitrogen is separated to (removing), add on this basis excessive water vapour and make it carry out transformationreation.
As installation for blast furnace gas, even the waste gas that contains carbon monoxide that produce continuously from metallurgical furnace instead of that produce off and on, also as described in detail in the application's the first invention, the organic substances such as plastic waste can be converted to geseous fuel, liquid fuel effectively.Even the waste gas that the metallurgical furnace producing continuously produces, the in the situation that of having flare stack, owing to inventing identical effect with the application second, also can reduce the burning amount of diffusing in this waste gas system.
On the other hand, in waste gas system, do not have the waste gas of metallurgical furnace generation of the continuous generation of flare stack, do not there is the effect of the direct minimizing burning amount of diffusing.But geseous fuel, the liquid fuel of manufacturing by method of the present invention is the fuel that can stably consume in the metal melting equipment of iron work etc., and has the feature that the combustions heat such as comparing installation for blast furnace gas is high.Its result is, improved the energy efficiency of metal melting equipment entirety, as its result, reduced the external fuel such as Sweet natural gas or the heavy oil amount of buying, and has and reduced the equal effect of the burning amount of diffusing.
Embodiment
[embodiment 1]
Example 1
On the gaseous emission pipe arrangement of the temporary transient gas-holder that stores converter gas, take-off pipe is set, can discharge section converter gas by this take-off pipe.In the downstream side of this take-off pipe, configuration flow adjustable valve, vapor mixer, preheater (mixed gas of converter gas and steam with), shift-converter (cylinder is vertical), modified-reaction device (external heat type rotary furnace), the modified-reaction that possesses liquid fuel trap generate gas cooling gas cooler successively.Be provided with the quantitative throwing device of plastic waste of screw transmission strap mode in the pan feeding side of above-mentioned modified-reaction device.In addition, on the exit side pipe arrangement of the exit side pipe arrangement of shift-converter and the cooling rear gas of gas cooler, be provided with thief hatch and under meter.
The average composition of the converter gas in gas-holder is H 2: 12 volume %, CO:54 volume %, CO 2: 17 volume %, H 2o:1 volume %, N 2: 16 volume %.To vapor mixer with 74Nm 3/ h supplies with converter gas, with 100Nm 3it is 10kg/cm as the pressure of water vapour that/h supplies with 2the steam of G, is warming up to 320 DEG C with preheater, is then imported shift-converter (being filled with Fe-Cr is high temperature shift catalysts).By the transformationreation in shift-converter, having obtained gas composition is H 2: 26 volume %, CO:2 volume %, CO 2: 28 volume %, H 2o:37 volume %, N 2: the gas (transformationreation generation gas) of 7 volume %.The flow that this transformationreation generates gas is 172Nm 3/ h (mass rate is 170kg/h), reactor outlet gas temperature are 430 DEG C.
Be heated in advance 500 DEG C as the external heat type rotary furnace of modified-reaction device, import transformationreation to this modified-reaction device and generate gas, the polyethylene simultaneously granulating as the break process of the model substance of plastic waste using 880kg/h supply, makes it be warming up to 800 DEG C of plan temperature of reaction.Reach after 800 DEG C, discharge the liquid resultant being trapped by liquid fuel trap, then, proceed the modified-reaction of 1 hour plastic waste.
According to obtaining the growing amount of geseous fuel composition and form by the cooled gasometry result of gas cooler, in addition, obtain liquid fuel composition growing amount and composition according to the analytical results of the liquid resultant being trapped by liquid fuel trap, in addition, obtain LHV for geseous fuel.These be the results are shown in to table 1.
Because transformationreation as raw material supplying generates gas and poly total amount is 1050kg/h, therefore, as follows with respect to the production rate of base feed total amount: geseous fuel is 36%, liquid fuel is 62%.Because be difficult to directly measure unreacted amount of polyethylene, therefore, if geseous fuel (380kg/h) and liquid fuel (650kg/h) are defined as to polyethylene decomposition rate with respect to the transformationreation generation gas of supplying with and the total yield of poly total amount (1050kg/h), in this example 1, polyethylene decomposition rate is 98%, is abundant high value, the hydrocarbon to generating more than C25 unconfirmed substantially, hence one can see that, and polyethylene is by degraded efficiently.By the modified-reaction of organic substance, H 2o, CO 2, H 2by completely consumed, can think and carry out water vapour upgrading, carbonic acid gas upgrading, hydrogenation, these four reactions of hydrocracking simultaneously.The LHV of the geseous fuel generating is 8.9Mcal/Nm 3, heat is increased to converter gas (1.9Mcal/Nm 3) 4.7 times.
[table 1]
* 1 transformationreation generates gas+polyethylene
Example 2～10
In the equipment identical with example 1, make the vapor flow rate of supplying with to shift-converter carry out various changes and be 800 DEG C and 500 DEG C of these two levels by modified-reaction Temperature Setting, in addition, similarly operate with example 1, carried out the transformationreation of converter gas and utilized transformationreation to generate the PE modified reaction experiment of gas.The results are shown in table 2 and Fig. 4～Fig. 8.
Shown in Fig. 4 is that transformationreation generates the relation between the water vapor concentration of gas and vaporization rate and the liquefied fraction of poly modification (temperature of reaction: 800 DEG C).Wherein, the growing amount (kg/h) that vaporization rate refers to geseous fuel generates the ratio of gas and poly total amount (kg/h) with respect to supplied with transformationreation, and the definition of geseous fuel is as shown in table 1, for from H 2to C4.Similarly, liquefied fraction refers to that the growing amount (kg/h) of liquid fuel generates the ratio of gas and poly total amount (kg/h) with respect to the transformationreation of supplying with, and the definition of liquid fuel is as shown in table 1, for from C5 to C24.Shown in Fig. 5 be transformationreation generate gas water vapor concentration and by the relation between poly modification (temperature of reaction: the 800 DEG C) geseous fuel obtaining and the LHV of liquid fuel.The LHV of the every volume under the standard state that wherein, the LHV of liquid fuel converts with the gas of liquid fuel represents.Shown in Fig. 6 is that transformationreation generates the water vapor concentration of gas and by the relation between PE modified polyethylene decomposition rate, is particularly illustrated in 500 DEG C of temperature of reaction identical with polyethylene decomposition rate at 800 DEG C.Shown in Fig. 7 is that transformationreation generates the relation between the gas concentration lwevel of gas and the hydrogen concentration of the geseous fuel that obtains by PE modified (temperature of reaction: 800 DEG C).Shown in Fig. 8 is that transformationreation generates the relation between the hydrogen concentration of gas and the gas concentration lwevel of the geseous fuel that obtains by PE modified (temperature of reaction: 500 DEG C).
Example 11
Fig. 9 illustrates the overview of the equipment using in this embodiment.This equipment possesses the vertical modified-reaction device 9 (internal volume: about 3m in bottom with gas dispersion plate 90 3), in this modified-reaction device 9, fill to orlop the polyethylene a that 880kg break process granulates, put at an upper portion thereof metal net b (10 order), filled again Ni catalyzer c (the Ni load factor: 10 quality %, carrier: α-Al of 800kg to its top 2o 3).The transformationreation generation gas being generated by shift-converter 8 is fed to the bottom of modified-reaction device 9, sees through gas dispersion plate 90 and is supplied in reactor, in reactor, rises.Modification resultant is discharged from the top of modified-reaction device 9, utilizes liquid fuel trap 10 to be separated into geseous fuel and liquid fuel.Geseous fuel after separation is cooling by gas cooler 11.It should be noted that, identical with example 1 to the device structure of shift-converter 8 from the gas-holder of temporary transient storage converter gas.
Use equipment as above, plan temperature of reaction in modified-reaction device 9 is set as to 750 DEG C, in addition, set the condition identical with example 1 (converter gas composition generates gas composition, temperature, flow etc. until obtain condition, the transformationreation of transformationreation generation gas), carried out PE modified reaction experiment.
Obtain growing amount and the composition etc. of geseous fuel composition, liquid resultant by the method identical with example 1.The results are shown in table 3.Obtain and the essentially identical reaction result of example 1, can think that the temperature of reaction in modified-reaction device 9 can be reduced to than the temperature of low 50 DEG C of example 1 (750 DEG C) is the effect of adding catalyzer.
[table 3]
* 1 transformationreation generates gas+polyethylene
Example 12
The waste gas producing as the metallurgical furnace that contains carbon monoxide, has used installation for blast furnace gas.Installation for blast furnace gas carries out the H that consists of after desulfurization, drying treatment 2: 3 volume %, CO:23 volume %, CO 2: 21 volume %, N 2: 53 volume %, therefore, carry out nitrogen separation by the PSA method of the following stated, improve the concentration of carbon monoxide.
Utilize PSA method nitrogen separate in, under normal pressure with 136Nm 3/ h is to being filled with the Cu of 400kg as sorbent material +the adsorption tower of load type active carbon is supplied with above-mentioned installation for blast furnace gas.Desorb is carried out under 7kPa (absolute pressure), desorption gas (=carbon monoxide concentrated after installation for blast furnace gas) consist of H 2: < 1 volume %, CO:47 volume %, CO 2: 37 volume %, N 2: 16 volume %, flow are 58Nm 3/ h.Installation for blast furnace gas after this carbon monoxide is concentrated and as the pressure 10kg/cm of water vapour 2the steam of G is respectively with 58Nm 3/ h, 73Nm 3/ h is supplied to vapor mixer, similarly carries out transformationreation with example 1.Its result is that obtaining gas composition is H 2: 19 volume %, CO:2 volume %, CO 2: 35 volume %, H 2o:37 volume %, N 2: the gas (transformationreation generation gas) of 7 volume %.
The flow that this transformationreation generates gas is 130Nm 3/ h (mass rate is 146kg/h), reactor outlet gas temperature are 430 DEG C.Except using this transformationreation generate gas and modified-reaction temperature is made as 600 DEG C, similarly carry out PE modified reaction with example 1.Reaction result is: geseous fuel growing amount is that 280kg/h, liquid fuel growing amount are that 590kg/h, polyethylene decomposition rate are 85%, the LHV of geseous fuel is 7.3Mcal/Nm 3, can confirm, utilize the installation for blast furnace gas after carbon monoxide concentrates also can efficiently react.In addition, because the LHV of installation for blast furnace gas is 770kcal/Nm 3, therefore can obtain the gas of 9 times of above combustions heat.
Comparative example 1
For to utilize water vapour and hydrogen concentration all the PE modified reaction efficiency of low gas study, made and consisted of H 2: 1 volume %, CO:61 volume %, CO 2: 19 volume %, H 2o:1 volume %, N 2: the standard gas of 18 volume %, utilizes this gas to carry out PE modified reaction experiment.Its result is, at 800 DEG C of temperature, polyethylene decomposition rate is 16%, vaporization rate is only 10%, liquefied fraction is only 5%, does not substantially carry out degraded.
[embodiment 2]
Example 13
To capacity 200,000 m 3gas-holder carry out diffusion combustion with one flare stack on be connected in the Zhi Gang factory of two converter 1a, 1b carrying out diverse blowing, carried out the shop test of method of the present invention.
The waste gas generation of converter 1a is 100,000 Nm 3/ hr, waste gas produces and continues 90 minutes, and blowing is spaced apart 90 minutes, and therefore, time-averaged waste gas generation is 50,000 Nm 3/ hr.The waste gas generation of another converter 1b is 120,000 Nm 3/ hr, waste gas produces and continues 20 minutes, and blowing is spaced apart 70 minutes, and therefore, time-averaged waste gas generation is 2.7 ten thousand Nm 3/ hr.Therefore, the average exhausted air quantity of total ascent time of converter 1a and converter 1b is 7.7 ten thousand Nm 3/ hr.Be provided with the pipe arrangement that each workshop in this iron work utilizes waste gas in the downstream of gas-holder, the exhaust gas utilization amount of total is 5.5 ten thousand Nm 3/ hr.
When the horizontal exceeding 95% of gas-holder, T-valve starts diffusion combustion towards flare stack side, then, is below 92% time in the level of gas-holder, finishes diffusion combustion.Shown in Figure 10 is to start until the gas-holder level after 6 hours changes and the burning amount of diffusing (instantaneous delivery) from certain time.According to Figure 10, because the accumulative total burning amount of diffusing is during this period 4.7 ten thousand Nm 3/ hr, therefore the time average burning amount of diffusing is 7700Nm 3/ hr, with the ratio of time average exhausted air quantity, diffusion combustion rate has reached 10%.
On the gaseous emission pipe arrangement of the temporary transient gas-holder that stores converter gas, take-off pipe is set, makes to pass through this take-off pipe discharge unit converter gas.In the downstream side of this take-off pipe, configuration flow adjustable valve, vapor mixer, preheater (mixed gas of converter gas and steam with), shift-converter (cylinder is vertical), modified-reaction device (external heat type rotary furnace), the modified-reaction that possesses liquid fuel trap generate gas cooling gas cooler successively.The quantitative throwing device of plastic waste of screw transmission strap mode is set in the pan feeding side of above-mentioned modified-reaction device.In addition, on the exit side pipe arrangement of the exit side pipe arrangement of shift-converter and the cooling rear gas of gas cooler, thief hatch and under meter are set.
The average composition of the converter gas in gas-holder is H 2: 12 volume %, CO:54 volume %, CO 2: 17 volume %, H 2o:1 volume %, N 2: 16 volume %.With 1770Nm 3/ hr supplies with converter gas to vapor mixer, with 2370Nm 3/ hr supplies with the pressure 10kg/cm as water vapour 2the steam of G, is warming up to after 320 DEG C by preheater, is imported in shift-converter (filling Fe-Cr is high temperature shift catalysts).By the transformationreation of shift-converter, having obtained gas composition is H 2: 26 volume %, CO:2 volume %, CO 2: 28 volume %, H 2o:37 volume %, N 2: the gas (transformationreation generation gas) of 7 volume %.The flow that this transformationreation generates gas is 4130Nm 3/ h (mass rate is 4.1t/hr), reactor outlet gas temperature are 430 DEG C.
Be heated in advance 500 DEG C as the external heat type rotary furnace of modified-reaction device, in this modified-reaction device, import transformationreation generation gas, the polyethylene simultaneously granulating as the break process of the model substance of plastic waste using 21t/hr supply, makes it be warming up to 800 DEG C of plan temperature of reaction.Reach after 800 DEG C, the liquid resultant being trapped by liquid fuel trap is discharged, then proceed the modified-reaction of 1 hour plastic waste.
According to obtaining the growing amount of geseous fuel composition and form by the cooled gasometry result of gas cooler, in addition, obtain liquid fuel composition growing amount and composition according to the analytical results of the liquid resultant being trapped by liquid fuel trap, in addition, obtain LHV for geseous fuel.These be the results are shown in to table 4.
Because transformationreation as raw material supplying generates gas and poly total amount is 25.1t/hr, therefore, as follows with respect to the production rate of base feed total amount: geseous fuel is 36%, liquid fuel is 62%.Owing to being difficult to directly to measure unreacted amount of polyethylene, therefore, if geseous fuel (9.05t/hr) and liquid fuel (15.65t/hr) are defined as to polyethylene decomposition rate with respect to supplied with transformationreation generation gas and the total yield of poly total amount (25.1t/hr), in this example 1, polyethylene decomposition rate is 98%, it is abundant high value, substantially the generation of the hydrocarbon more than C25 unconfirmed, hence one can see that, and polyethylene is by effectively degraded.By the modified-reaction of organic substance, H 2o, CO 2, H 2by completely consumed, can think and carry out water vapour upgrading, carbonic acid gas upgrading, hydrogenation, these four reactions of hydrocracking simultaneously.The LHV of the geseous fuel generating is 8.9Mcal/Nm 3, heat is increased to converter gas (1.9Mcal/Nm 3) 4.7 times.
[table 4]
* 1 transformationreation generates gas+polyethylene
Shown in Figure 11 be this shop test time gas-holder level change and the burning amount of diffusing, shown in Figure 12 is the burn variation of the amount of diffusing of the accumulative total of being tried to achieve by Figure 10 (conventional example) and Figure 11 (inventive example).From Figure 11 and Figure 12, the application of the invention method, the accumulative total burning amount of diffusing is reduced to 3.5 ten thousand Nm 3/ hr.Thus, the time average burning amount of diffusing is reduced to 5800Nm 3/ hr, burning bleeding rate is reduced to 7.6%, and effect of the present invention is clear and definite.The time average burning amount of diffusing in the past shown in Figure 10 is 7700Nm 3/ hr, the burning amount of diffusing has reduced 1900Nm with time average 3/ hr (is equivalent to 1,600 ten thousand Nm 3/ year).Converter gas is 1770Nm to the discharge of shift-converter 3/ hr, the actual value of the burning amount of diffusing increases slightly, but can think the error being produced by the time average of trying to achieve the burning amount of diffusing than the variation of short period.

Claims (8)

1. a degraded method for organic substance, the method comprises:
Make it carry out transformationreation by add excessive water vapour in the waste gas that contains carbon monoxide (g0) producing in metallurgical furnace, the mixed gas (g) of water vapour that formation contains hydrogen that transformationreation generates and carbonic acid gas and do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, organic substance modification is carried out degraded, water vapor concentration is that 5～70 volume %, hydrogen concentration are that 10～40 volume %, gas concentration lwevel are 10～40 volume % in described mixed gas (g).
2. the degraded method of organic substance according to claim 1, wherein, waste gas (g0) is, the waste gas that contains carbon monoxide and nitrogen by producing from metallurgical furnace, at least a portion nitrogen is separated to the waste gas that has improved carbon monoxide concentration.
3. the degraded method of organic substance according to claim 1 and 2, wherein, the organic substance for the treatment of modification is to be selected from more than one in plastic waste, oil-containing mud, waste oil.
4. a manufacture method for fuel, the method comprises:
The modifier of the organic substance that the degraded method of the organic substance by described in any one in claim 1～3 is obtained reclaims with the form of geseous fuel and/or liquid fuel.
5. the waste gas that metallurgical furnace produces utilize a method, the method comprises:
At the gas-holder with the waste gas that contains carbon monoxide (g0) that temporary transient storage produces off and on from metallurgical furnace, the waste gas (g0) that is stored in this gas-holder is delivered to gas and is utilized the pipe arrangement of supplying gas of equipment, carry out in the exhaust gas apparatus of flare stack of diffusion combustion with the waste gas (g0) that can not be stored in gas-holder, by a part of pipe arrangement combustion gas (g0) that supply gas from the described pipe arrangement branch of supplying gas, make it carry out transformationreation to the excessive water vapour of the middle interpolation of this waste gas (g0), formation contains hydrogen and the carbonic acid gas that transformationreation generates, mixed gas (g) with the water vapour not consuming in transformationreation, this mixed gas (g) is contacted with organic substance, organic substance modification is carried out degraded, in described mixed gas (g), water vapor concentration is 5～70 volume %, hydrogen concentration is 10～40 volume %, gas concentration lwevel is 10～40 volume %.
6. the waste gas that metallurgical furnace according to claim 5 produces utilize method, wherein, add excessive water vapour make its waste gas that carries out transformationreation (g0) be by from metallurgical furnace produce the waste gas that contains carbon monoxide and nitrogen at least a portion nitrogen is separated to the waste gas that has improved carbon monoxide concentration.
7. the waste gas producing according to metallurgical furnace described in claim 5 or 6 utilize method, wherein, the organic substance for the treatment of modification is to be selected from more than one in plastic waste, oil-containing mud, waste oil.
8. a manufacture method for fuel, the method comprises:
The modifier of the organic substance obtaining by the method described in any one in claim 5～7 is reclaimed with the form of geseous fuel and/or liquid fuel.
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JP6197266B2 (en) * 2012-03-27 2017-09-20 Ｊｆｅスチール株式会社 Method for producing modified coal
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CN116463148A (en) * 2023-04-20 2023-07-21 北京科技大学 Method and device for producing hydrogen by blowing steam-coke powder into converter flue

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101796168A (en) * 2007-08-01 2010-08-04 龙树能源私人有限公司 A process for producing small molecular weight organic compounds from carbonaceous material

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56108816A (en) * 1980-02-02 1981-08-28 Nippon Steel Corp Conversion recovery method of exhaust gas of refining furnace
JPS62278770A (en) * 1986-05-27 1987-12-03 Nippon Kokan Kk <Nkk> Recovering method of co2 and h2 from converter gas
JPS62278769A (en) * 1986-05-27 1987-12-03 Nippon Kokan Kk <Nkk> Recovering method of co2 and h2 from converter gas
JP2000283658A (en) * 1999-03-30 2000-10-13 Kawasaki Steel Corp Method and apparatus for utilizing converter gas
JP2001131560A (en) * 1999-11-09 2001-05-15 Hitachi Ltd Method and apparatus for thermally decomposing hydrocarbon raw material
JP2002212575A (en) * 2001-01-16 2002-07-31 Nippon Steel Corp High-level treating apparatus for purified coke oven gas and utilization method
JP2006063290A (en) * 2004-08-30 2006-03-09 Ebara Corp System and method for utilizing polymer hydrocarbon
US7932424B2 (en) * 2006-01-26 2011-04-26 Kitakyushu Foundation For The Advancement Of Industry, Science And Technology Method for catalytically cracking waste plastics and apparatus for catalytically cracking waste plastics
JP5476792B2 (en) * 2008-05-16 2014-04-23 Ｊｆｅスチール株式会社 Method for reforming exhaust gas generated from metallurgical furnace, reformer, and method for producing reformed gas

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101796168A (en) * 2007-08-01 2010-08-04 龙树能源私人有限公司 A process for producing small molecular weight organic compounds from carbonaceous material

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