CN103154201A - 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

Info

Publication number
CN103154201A
CN103154201A CN2011800479237A CN201180047923A CN103154201A CN 103154201 A CN103154201 A CN 103154201A CN 2011800479237 A CN2011800479237 A CN 2011800479237A CN 201180047923 A CN201180047923 A CN 201180047923A CN 103154201 A CN103154201 A CN 103154201A
Authority
CN
China
Prior art keywords
gas
organic substance
volume
waste
transformationreation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800479237A
Other languages
Chinese (zh)
Other versions
CN103154201B (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
JFE Engineering Corp
Original Assignee
NKK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NKK Corp filed Critical NKK Corp
Publication of CN103154201A publication Critical patent/CN103154201A/en
Application granted granted Critical
Publication of CN103154201B publication Critical patent/CN103154201B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

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 with the organic substance modification, is used 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 used for reducing the burning amount of diffusing (the combustion baked amount of diffusing of the waste gas that is produced by metallurgical furnace, combustion diffusion quantity), described waste gas effectively is used in following technique: be used for making it degraded the organic substance modification 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, produce CO during burning disposal 2Deng and high to environmental pressure, but also have the problem of the thermal damage of incinerator, seek to establish chemical reutilization technology.
In chemical reutilization technology, as the technology that is used for organic substance is converted to geseous fuel or liquid fuel, carried out at present various researchs centered by plastic waste, and the scheme below for example having proposed.
A kind of method is disclosed in patent documentation 1, its by more than making hydrogen concentration 60 volume %, more than preferred 80 volume %, the organic substances such as the coke-fired furnace gas (COG) of temperature more than 600 ℃ and plastic waste react, with high-level efficiency with organic substance hydrocracking, aerification, with the COG gain of heat.
In addition, patent documentation 2 discloses a kind of method, and it uses the mobile contact catalyst (FCC) of oil as the thermal medium catalyzer of holding concurrently, and at 350～500 ℃ of temperature, plastic waste is decomposed and be converted to liquid fuel.
In addition, a kind of method is disclosed in patent documentation 3, it is when carrying out thermolysis to RDF or timber etc., the gas that thermolysis is generated carries out the water vapour upgrading, make gas after by this water vapour upgrading, hydrogen concentration being improved in the circulation of thermolysis section, carry out thermolysis in having improved the atmosphere after the hydrogen concentration.
The 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.
At first, about patent documentation 1, hydrogen concentration in COG is more than 60 volume %, even also only limit to destructive distillation latter stage in dry distillation of coal operation, therefore, in the method for patent documentation 1, need at the destructive distillation moment switching gas flow path in latter stage, supply with the COG more than 600 ℃ that contains a large amount of dust in plastic waste hydrocarbon hydrocracking reaction device.But, under harsh like this condition, be difficult to make flow channel switching valve continuous firing steadily in the long term, on this meaning, can say that this technology lacks realization property.In addition, in order to realize the available gas of plastic waste, need to supply with the COG that contains the 60 above hydrogen of volume % continuously in the hydrocarbon hydrocracking reaction device, for this reason, need to hydrogen concentration meter and flow channel switching valve all be 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 the 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 that generates with 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 that is used for the organic substances such as plastic waste are converted to geseous fuel, liquid fuel, there is problem as above, the expectation proposition relates to the scheme of the degraded method of organic substance, the degraded method of this organic substance can use can stable supplying gas with organic substance modification and carry out degraded effectively, thereby it is few and contain the modifier of a large amount of light compositions to obtain heavy ingredient and carbonaceous, and can utilize fairly simple equipment to implement.
On the other hand, there is following problem at present in effective utilization of the waste gas that produces about metallurgical furnace.That is, the various metallurgical furnaces that carry out batch production such as converter 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 generation CO concentration is the waste gas about 50～70 volume %.But, because duration of blast is about 10～30 minutes, be 100,000 Nm at for example instantaneous delivery 3In the situation of/hr, comprise that the time average flow of the time of blowing is not 1.7～50,000 Nm 3/ hr left and right.Because low-burning heat is 2000kcal/Nm 3The left and right, therefore, converter gas is used effectively as 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 can't be accommodated into the moment of gas-holder fully, and existence must be carried out from flare stack the problem of diffusion combustion.
For such problem, using method as the converter gas of the diffusion combustion that be used for to suppress 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, utilize CO in converter gas as the raw material of acetic acid.
But acetic acid is not necessary auxiliary material at iron work, because need to carry out outer selling, when lacking the demand of acetic acid, needs to reduce its manufacture, and 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 degraded and when being converted to geseous fuel, liquid fuel etc. with organic substances such as plastic waste, can use can stable supplying gas with organic substance modification and carry out degraded effectively, thereby it is few and contain the modifier of a large amount of light compositions to obtain heavy ingredient and carbonaceous, 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 that produces 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.At first, in order to solve the first problem, following method is effective: add excessive water vapour in the waste gas that contains carbon monoxide that produces in the metallurgical furnace and make it carry out transformationreation, 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, carry out the organic substance modification of high molecular degraded.In addition we know, there is preferred scope in this organic substance modification with the composition of mixed gas (transformationreation generation gas).
In addition we know, the waste gas that produces by the metallurgical furnace that will contain carbon monoxide effectively utilizes as the unstripped gas that organic substance is carried out degraded special process as above, can solve the second problem.Namely, geseous fuel, liquid fuel that the gas that produces by the metallurgical furnace that will contain carbon monoxide obtains as the unstripped gas of the degraded technique of specific organism as described above, integral in the metal melting equipment of iron work etc., owing to being the fuel that often is consumed, so need not to reduce as required its manufacture, therefore, the gas that metallurgical furnace produces stably can be used (consumption) as unstripped gas, so, can stably reduce the burning of gas amount of diffusing that metallurgical furnace produces.
The present invention is based on above-mentioned opinion and completes, and its purport is as follows.
[1] a kind of degraded method of organic substance, the method comprises: by the waste gas (g that contains carbon monoxide that produces in metallurgical furnace 0) in add excessive water vapour and make it carry out transformationreation, formation contains hydrogen that transformationreation generates and carbonic acid gas and the mixed gas (g) of the water vapour that do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, carry out the organic substance modification degraded.
[2] the degraded method of above-mentioned [1] described organic substance, wherein, waste gas (g 0) be by in the waste gas that contains carbon monoxide and nitrogen that produces, at least a portion nitrogen is separated the waste gas that has improved carbon monoxide concentration from metallurgical furnace.
[3] the degraded method of above-mentioned [1] or [2] described organic substance, wherein, the water vapor concentration of mixed gas (g) is 5～70 volume %.
[4] the degraded method of above-mentioned [3] described organic substance, 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 described organic substance of 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] a kind of manufacture method of fuel, the method comprises: the modifier of the organic substance that will obtain by the degraded method of the described organic substance of any one in above-mentioned [1]～[5] reclaims with the form of geseous fuel and/or liquid fuel.
[7] waste gas that produces of a kind of metallurgical furnace utilize 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 the pipe arrangement and can not be stored in the waste gas (g of gas-holder of supplying gas that gas utilizes 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 and make it carry out transformationreation, formation contains hydrogen that transformationreation generates and carbonic acid gas and the mixed gas (g) of the water vapour that do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, carry out the organic substance modification degraded.
[8] above-mentioned [7] described method wherein, is added excessive water vapour and is made it carry out the waste gas (g of transformationreation 0) be by the waste gas that contains carbon monoxide and nitrogen that produces from metallurgical furnace, at least a portion nitrogen being separated the waste gas that has improved carbon monoxide concentration.
[9] above-mentioned [7] or [8] described method, 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] the described method of 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] a kind of manufacture method of fuel, the method comprises: the modifier of the organic substance that will obtain by the described method of any one in above-mentioned [7]～[11] reclaims with the form of geseous fuel and/or liquid fuel.
The effect of invention
According to the application's the first invention, the organic substance of the high molecular such as plastic waste is degraded and when 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 heavy ingredient or carbonaceous few and contain the high calorie modifier of 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 also can carry out the modification of organic substance under lower temperature of reaction, therefore, can utilize fairly simple equipment to implement.In addition, the CO that generates 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, according to the application second invention, the waste gas that the metallurgical furnace that contains carbon monoxide as the lower waste gas of heat can be produced effectively utilizes 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.Geseous fuel, liquid fuel are indispensable in the metal melting equipment of iron work etc., stablized the fuel of consumption, thereby need not as required and reduce manufacture, therefore, the waste gas that metallurgical furnace produces stably can be used (consumption) as unstripped gas, thus, the burning amount of diffusing of the waste gas of metallurgical furnace generation is stably reduced.Particularly in the metal melting equipment of iron work etc., generation and fuel consumption, the turnout in equipment of the waste gas that metallurgical furnace produces are proportional, therefore the generation of the waste gas of metallurgical furnace generation is also proportional with the usage quantity of the waste gas of the metallurgical furnace generation that is used for fuel making, from this side considerations, the burning amount of diffusing of the waste gas of metallurgical furnace generation is stably reduced.
In addition, processing aspect from organic substances such as plastic waste, the organic substance of the high molecular such as plastic waste is degraded and when being converted to geseous fuel, liquid fuel etc., can use can stable supplying the waste gas that produces of metallurgical furnace effectively the modification organic substance and carry out degraded, thereby obtain heavy ingredient and carbonaceous few and contain the high calorie modifier of 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 also can carry out the modification of organic substance under lower temperature of reaction, therefore, can utilize fairly simple equipment to implement.In addition, the CO that generates by transformationreation 2Can be when the modification of organic substance being changed to CO in the reaction of carbonic acid gas upgrading, therefore, can implementing the chemistry recycling of organic substance and do not make CO 2Generation increases.
Description of drawings
[Fig. 1] is the graphic representation that is illustrated in the relation between the addition of water vapour in the transformationreation of adding water vapour in the converter gas and carrying out and the gas composition after transformationreation (temperature 430 ℃ under equilibrium composition calculated value);
[Fig. 2] is the structure iron of exhaust gas apparatus that the converter of existing general iron work is shown;
[Fig. 3] is the structure iron that illustrates be used to an embodiment implementing equipment of the present invention;
[Fig. 4] is water vapor concentration and the vaporization rate in poly modification (degraded) and the graphic representation of the relation between liquefied fraction that transformationreation generation gas in embodiment 1 is shown;
[Fig. 5] is the graphic representation that the relation between the LHV that transformationreation in embodiment 1 generates the water vapor concentration of gas and the geseous fuel that obtains by poly modification (degraded) and liquid fuel is shown;
[Fig. 6] illustrates the water vapor concentration of transformationreation generation gas in embodiment 1 and the graphic representation of the relation between the polyethylene decomposition rate in poly modification (degraded);
[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 and the passing of the burning amount of diffusing in the example of embodiment 2 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
The A treatment facility
The a polyethylene
The b net
C Ni catalyzer
Embodiment
At first, the degraded method of the organic substance of the application first invention described.
Waste gas (the g that contain carbon monoxide of method of the present invention by producing to metallurgical furnace 0) (below, be sometimes referred to as " metallurgical furnace produce waste gas ") add excessive water vapour and make it carry out transformationreation, formation contains the mixed gas (g) of the water vapour that does not consume in hydrogen that transformationreation generates and carbonic acid gas and transformationreation, make this mixed gas (g) (below, be sometimes referred to as " transformationreation generation gas ") contact with organic substance, carry out the organic substance modification degraded.Need to prove, to waste gas (g 0) in add excessive water vapour and refer to add water vapour in the mode that the remaining water vapour that does not consume remains in mixed gas (g) in transformationreation.
For such method of the present invention, even also can effectively promote the degraded of organic substance under lower temperature of reaction, the hydrogen consumption is also few, and the almost generation to heavy ingredient and carbonaceous unconfirmed.
The contour molecular weight organic material of known plastic waste can begin thermolysis usually when heating more than 300～400 ℃, at this moment, carrying out lighting simultaneously, also can carry out heaviness.If when thermolysis, hydrogen is coexisted, carry out hydrogenation reaction and hydrocarbon hydrocracking reaction to the 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 the 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 that is modified.In method of the present invention, even also can effectively promote the degraded of organic substance under lower temperature of reaction, the hydrogen consumption is also few, and the almost generation to heavy ingredient and carbonaceous unconfirmed, this can think owing to carrying out the modification (degraded) of organic substance and carrying out simultaneously hydrogenation, hydrocracking, water vapour upgrading, these four reactions of carbonic acid gas upgrading by the above-mentioned mixed gas of use (g).
For example, the waste gas that produces from metallurgical furnaces such as converters, usually contain the CO about 25～80 volume %.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 after transformationreation (g), comprise the H that generates 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 simultaneously hydrogenation, hydrocracking, water vapour upgrading, these four reactions of carbonic acid gas upgrading of each gaseous constituent.
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 substance modification with mixed gas (g).But, 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 that for example, uses) in iron work 2: 10～20 volume %, N 2: 10～20 volume %, H 2: about 0～5 volume % (containing in addition saturated steam), therefore, the general reactivity that does not need to carry out transformationreation is controlled, can be only extra proportion by adjustment water vapour each concentration of the water vapour in mixed gas (g), hydrogen, carbonic acid gas is controlled at desired level.
Need to prove, the reactivity of transformationreation can be controlled by the residence time that is adjusted in shift-converter.For example, in order to shorten the residence time, usually adopt the method that reduces shift-converter length or reduce the catalyzer loading level, in this situation, shift-converter length and catalyzer loading level can be set as and react 1/2～1/4 left and right that proceeds to when 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 ℃ under equilibrium composition calculated value).Hence one can see that, can control by only adjusting the 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 usually is performed until to react and reaches in a basic balance.
Below, details and the preferred condition of method of the present invention described.
In the present invention, as the waste gas (g that carries out transformationreation 0) using the reasons are as follows of waste gas that metallurgical furnace produces: the waste gas that metallurgical furnace produces contains carbon monoxide with higher concentration, and the concentration of unwanted nitrogen is low.Waste gas (g as the metallurgical furnace generation that contains carbon monoxide 0), can use waste gas arbitrarily.The most representative is the converter gas that is produced by the converter of the decarbonization process that carries out the iron and steel manufacturing process, in addition, the waste gas such as generation from change iron preprocessing furnace, fusion reducing furnace, shaft furnace etc. can be enumerated, one or more the mixed gas in these waste gas can be used.
The carbon monoxide that generates in metallurgical technology further oxidized and generate carbonic acid gas ratio, be post-combustion rate (CO 2/ (CO+CO 2) * 100) usually nothing but 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 about 0～20 volume %.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, and the composition that needs only gas is 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 (transformationreation, hydrogenation, hydrocracking, water vapour upgrading, carbonic acid gas upgrading) that occurs in the present invention, on the other hand, geseous fuel to manufacturing dilutes, low-burning heat (below, be called " LHV ") is reduced.Particularly, if nitrogen concentration surpasses 50 volume %, the LHV of geseous fuel significantly reduces, and also there is the tendency of reduction in transformationreation speed.Therefore, nitrogen concentration preferably is in above-mentioned compositing range.
Narrate as the front, the composition that is stored in the waste gas that the metallurgical furnace of gas-holder (the general gas-holder that for example, uses) produces in iron work is generally CO:50～70 volume %, CO 2: 10～20 volume %, N 2: 10～20 volume %, H 2: about 0～5 volume % (in addition, comprising saturated steam), this composition is equivalent to high CO concentration and forms in the composition of the waste gas that above-mentioned general metallurgical furnace produces.Gas is used because each factory in iron work acts as a fuel to be stored in gas in gas-holder, therefore, need to prevent the reduction in the efficiency of combustion of utilizing the place.Therefore, the reason that the lower value of CO concentration in gas is set as the storage requirement in gas-holder is to form because formed high CO concentration.
In the present invention, be no matter the composition that is stored in the waste gas that the higher waste gas of CO concentration such in common gas-holder or common metallurgical furnace as above produce that uses in iron work, can be as waste gas (g 0) be used.
But, at the waste gas (g of metallurgical furnace generation 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 separate (removing) and after having improved carbon monoxide concentration at least a portion of the nitrogen that will contain, 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 the nitrogen concentration in waste gas surpasses 30 volume %, the nitrogen separation circuit preferably is 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 and separate, can enumerate installation for blast furnace gas, in addition, can also enumerate waste gas that the shaft furnace of electric furnace or operation under the condition that nitrogen concentration increases produces etc.In addition, also can carry out nitrogen for the waste gas that contains the higher concentration carbon monoxide as converter gas etc. and separate, after further improving 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 the CO sorbent material and known load has Cu +Also CO absorption of gac 2, therefore can be by with load, Cu being arranged +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 are with the separation of the nitrogen 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, the waste gas (g that produces to metallurgical furnace in advance 0) in add water vapour, and it imported in the fixed-bed reactor of having filled catalyzer carry out transformationreation.In addition, also can add in advance part water vapour, and add catalyzer by the multistage in reactor, then from adding remaining water vapour between catalyst layer and catalyst layer.
In addition, if the waste gas (g that produces to metallurgical furnace respectively 0) in add water vapour, hydrogen, carbonic acid gas and do not carry out as the present invention transformationreation, the organic substance modification that also can obtain and obtain in the transformationreation of the present invention gas of mixed gas (g) same composition, 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 modification that is obtained by transformationreation comprises water vapour, hydrogen and carbonic acid gas with mixed gas (g), and their concentration is not particularly limited, but due to following reason, the preferably water vapor concentration is 5～70 volume %.Namely, 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 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 be 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 CO in gas 2Residual, in addition, the LHV that can also suppress geseous fuel, liquid fuel reduces.
In addition, consider from the viewpoint of the rate of decomposition of guaranteeing organic substance, more than the hydrogen concentration in mixed gas (g) and gas concentration lwevel all are preferably 5 volume %.
In addition, due to following reason, the organic substance modification is with the preferred water vapor concentration that consists of of mixed gas (g): 20～70 volume %, hydrogen concentration: 10～40 volume %, gas concentration lwevel: 10～40 volume %.Need to prove, also can contain other gaseous constituent (such as nitrogen etc.) in this mixed gas (g).More than water vapor concentration being made as 20 volume %, can fully improving the rate of decomposition of organic substance, and can improve the LHV of geseous fuel.Reason such as front that water vapor concentration is made as below 70 volume % are narrated.By (more preferably more than 12 volume %) more than hydrogen concentration being made as 10 volume %, particularly in the situation that than carrying out the modified-reaction of organic substance under lower temperature, also can be suppressed at residual CO in geseous fuel 2By (more preferably more than 13 volume %) more than gas concentration lwevel being made as 10 volume %, be difficult for residual heat than hydrocarbon and the low gaseous constituent H of CO in geseous fuel 2In 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, also can contain other gaseous constituent (such as nitrogen etc.) in this mixed gas (g).
In addition, as one of feature of the present invention, can enumerate geseous fuel growing amount in the modification that to control organic substance by the organic substance modification with the water vapor concentration of mixed gas (g) and the ratio of liquid fuel growing amount.Namely, if more than the water vapor concentration of mixed gas (g) is set as 50 volume %, mainly generate geseous fuel (namely, geseous fuel growing amount＞liquid fuel growing amount), if water vapor concentration is made as below 40 volume %, mainly generate liquid fuel (that is, geseous fuel growing amount＜liquid fuel growing amount).Need to prove, the impact of hydrogen concentration, gas concentration lwevel is so remarkable not as the impact of water vapor concentration, as long as therefore be in preferable range of the present invention.
Below, the condition of the mixed gas (g) that adopts transformationreation to obtain being carried out the modification (degraded) of organic substance describes.
In the present invention, the organic substance as the object degraded by modification is not particularly limited, but the organic substance of preferred high molecular for example, can be enumerated plastic waste, oil-containing mud, waste oil etc., and more than one that can be in them are as object.
Here, oil-containing mud refers to the mixture of the sludge-like that produces in the 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, (be used for the organic substance modification is made its degraded reactor in order to improve to the modified-reaction device, lower with) operability when supplying with oil-containing mud etc., also can make moisture in mud be reduced to 30～50 quality % left and right by methods such as centrifugations.
In addition, as waste oil, can enumerate such as the various mineral oil that use, natural and/or synthetic oil lipid, various fatty acid esters etc., but be not limited to these.In addition, also can be the two or more mixture in above-mentioned waste oil.In addition, during for the waste oil that produces, generally contain the moisture of a large amount of (are generally surpass 80 quality % left and right) in the rolling process of iron work, from the 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 the modified-reaction device, therefore, the water vapour of considering this part decides the extra proportion of the water vapour that adds in transformationreation.
In addition, if plastic waste contains the chlorine-containing resins such as polyvinyl chloride, produce chlorine in the modified-reaction device, this chlorine may be included in geseous fuel, liquid fuel.Therefore, in the situation that plastic waste may contain chlorine-containing resins, preferably drop in the modified-reaction device as CaO etc. the chlorine absorption agent so that chlorine-containing component not in the geseous fuel of generation, liquid fuel.
Temperature of reaction during preferred organic substance modification is according to the following setting of kind of organic substance.In the situation that plastic waste, temperature of reaction is that 400～900 ℃ of left and right are more suitable.Temperature of reaction is during lower than 400 ℃, and the rate of decomposition of plastic waste is low, and on the other hand, if temperature of reaction surpasses 900 ℃, the generation of carbonaceous increases.In addition, in the situation that oil-containing mud or waste oil, temperature of reaction is that 300～800 ℃ of left and right are more suitable.During lower than 300 ℃, the rate of decomposition of oil-containing mud or waste oil reduces in temperature of reaction.On the other hand, temperature of reaction surpasses 800 ℃, and is without impact, but because be required above high temperature, uneconomical on modification (degraded) characteristic of oil-containing mud or waste oil.In addition, in the situation that take the mixture of plastic waste and oil-containing mud and/or waste oil as object, from the point of view, temperature of reaction is that 400～800 ℃ of left and right are more suitable.In addition, temperature of reaction does not have impact substantially on the ratio of geseous fuel growing amount and liquid fuel growing amount.In addition, also basically unconfirmed to the impact of pressure on it, therefore, make the modified-reaction device at normal pressure or a few kg/cm 2Little the adding of left and right, depressed comparatively economy of running.
The kind of modified-reaction device is not particularly limited, and moves smoothly in reactor from organic substances such as plastic waste, and can effectively contact aspect consideration, preferably the Horizontal mobile hearth reactor as rotary kiln with mixed gas (g) with the organic substance modification.
In addition, in the present invention, do not need especially catalyzer in the modification of organic substance, but can react by catalyst filling yet.As catalyzer, can use have 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 known dust that comprises the converter generation of fine Fe particle also can be used as modified catalyst or hydrocracking catalyst.
In the situation that catalyst filling from organic substances and the good aspect consideration of contacting of catalyzer such as plastic waste, can adopt so horizontal moving-bed type modified-reaction devices such as vertical modified-reaction device rather than rotary kiln.In this situation, the mixed gas that obtains in transformationreation (g), moving-bed type modified-reaction device.In this situation, compare with the situation of supplying with the mixed gas (g) that obtains from the top of modified-reaction device transformationreation, from the bottom and/or sidepiece when supplying with the mixed gas (g) obtain transformationreation, mixed gas (g) is better with contacting of organic substance or catalyzer, therefore preferred.
As vertical modified-reaction device, can use the common fixed-bed reactor that use in chemical industry, particularly in the situation that adopt mode from modified-reaction device underfeed mixed gas (g), can use blast furnace, shaft furnace or converter as ironmaking equipment as the modified-reaction device.In the situation that blast furnace, shaft furnace are used as the modified-reaction device, if be made into following moving-bed type, reaction efficiency increases, thereby preferred, 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 the stove bottom.In addition, in the situation that converter is used as the modified-reaction device, the intermittent reaction form that can make and blow identical, namely, after in organic substance and catalyzer are put into stove, supply with continuously mixed gas (g) from the 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 of the hydrocarbon of carbon monoxide and C1～C4, and its LHV is about 6～10Mcal/Nm 3So, it has following feature: although its LHV and Sweet natural gas are equal to, because carbon monoxide concentration is high, compare with natural-gas, its incendivity is high.High and incendivity is high due to carbon monoxide concentration, consider from the security aspect, 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.
Therefore liquid fuel is made of the hydrocarbon of C5～C24, is that (((mixture of C13～C24) is not for substantially containing the lightweight oil of the high-quality that is equivalent to heavy oil (more than C25) for C9～C12), light oil for C5～C8), lam-oil for petroleum naphtha.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 substitute reductive agent as the heavy oil of the fuel of such factory with metallurgical furnace such as iron work or ore hearth with the form of mixture.
Need to prove, (containing ratio of C5～C8) is many, except using as light liquid fuel, also can use as the chemical industry raw material after with petroleum naphtha composition fractionation by distillation due to petroleum naphtha.To this, can enumerate the method for utilizing of the petroleum naphtha composition after fractionation by distillation being carried out catalytic modification and being converted to benzene,toluene,xylene etc.
Utilize the modifier of the organic substance that method of the present invention obtains after modified-reaction is generated gas cooling, to be separated into respectively geseous fuel and liquid fuel by gas-liquid separation.In addition, can isolate as required petroleum naphtha, lam-oil, light oil by fractionation by distillation from liquid fuel.Method of cooling, gas-liquid separating method and distillation separation method that modified-reaction generates gas can carry out with known method, are not particularly limited.
In addition, consider from the above aspect, as long as use the mixed gas of mixed gas (g) same composition that obtains with the present invention, decomposing organic matter matter and make it degraded effectively just.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.Need to prove, also can contain other gaseous constituent (such as nitrogen etc.) in this mixed gas.
The reason that limits such gas composition is 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 to add more than one in water vapour, hydrogen, carbonic acid gas in basic gas.
Utilize the condition of modification (degraded) of the organic substance that this mixed gas carries out identical with the condition of the modification (degraded) of the invention described above method.
Therefore, the purport of the method such 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, carries out the organic substance modification 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 that will obtain by any method in above-mentioned [i]～[iii] reclaims with the form of geseous fuel and/or liquid fuel.
Below, the method for utilizing of the waste gas that the metallurgical furnace that the application second is invented produces describes.
Various metallurgical furnaces a large amount of waste gas of intermittent generation when producing of batch production is carried out in converters etc.For example, converter is take instantaneous delivery as 10～300,000 Nm 3/ hr left and right generation CO concentration is the waste gas about 30～70 volume %.But, because duration of blast is about 10～30 minutes, therefore, at interior time average under meter, be only 1.7～50,000 Nm with time of comprising not blowing 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 3Therefore the left and right 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, becomes in fact and the unbalanced state of instantaneous delivery.Therefore, have following problem: existence can not be accommodated into the moment of gas-holder fully, 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, with gas-holder 5 (for example, the gas-holder that possesses movable piston formation and volume-variable in inside that Wei Jinsi (Wiggins) formula gas-holder is such) as snubber, pipe arrangement 6 utilizes equipment 7 to supply gas to each gas in iron work by supplying gas.At this moment, 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 fully, therefore, T-valve 3 is switched to flare stack 4 sides, and waste gas is carried out diffusion combustion.Particularly in the situation that the blowing of another not shown converter is overlapping, owing to forming very large instantaneous delivery, therefore become the state that to avoid diffusion combustion.
In order to reduce the burning amount of diffusing, as mentioned above, the exhaust gas utilization amount that increases in iron work is comparatively effective, but iron work at home particularly is difficult to utilize to heavens waste gas, thereby merely increases utilization.
But, for blow into blast furnace and to oneself generating field that will smelt iron that waste gas acts as a fuel with the gain of heat of fuel gas 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 the exhaust gas utilization amount, its result can reduce the burning amount of diffusing.
Therefore, in the present invention, in gas recovery unit, will be by the pipe arrangement combustion gas (g that supplies gas by the above-mentioned pipe arrangement branch of supplying gas 0) a part, and unstripped gas that be converted to the above-mentioned special process (the degraded method of the organic substance of the application first invention of narrating previously) of geseous fuel, liquid fuel etc. is used as the organic substances such as plastic waste being carried out degraded with it, and described gas recovery unit has: temporarily store as above from the intermittent waste gas (g that contains carbon monoxide that produces of metallurgical furnace 0) (below, be sometimes referred to as " metallurgical furnace produce waste gas ") 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.That is, by to waste gas (g 0) in add excessive water vapour and make it carry out transformationreation, formation contains hydrogen that transformationreation generates and carbonic acid gas and the mixed gas (g) of the water vapour that do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, carry out the organic substance modification degraded.
Like this, use by unstripped gas that be converted to the special process of geseous fuel, liquid fuel etc. as the organic substances such as plastic waste being carried out degraded for the present invention's waste gas that metallurgical furnace is produced.Geseous fuel, liquid fuel are indispensable in the metal melting equipment of iron work etc., it stably is consumed, therefore need not to reduce as required its manufacture, therefore, the waste gas that metallurgical furnace produces stably can be used (consumption) as unstripped gas, thus, can also stably reduce the burning amount of diffusing of the waste gas of metallurgical furnace generation.
Need to prove, the feature of the degraded processing of the organic substance that carries out in the present invention and advantage such as front are described in the degraded method of the organic substance of the application's the first invention.
Fig. 3 is the pie graph be used to an embodiment 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 organic substance is degraded and be converted to the processing of geseous fuel and liquid fuel, the 8th, consist of the shift-converter of this treatment facility A, 9 are similarly the modified-reaction device.
With Fig. 2 similarly, the waste gas (g that discharges from converter 1 0) reclaimed by gas recovery unit 2, as snubber, utilize equipment 7 to supply gas by the pipe arrangement 6 of supplying gas to each gas in iron work gas-holder 5, by the waste gas (g from the pipe arrangement 60 discharging requirements of supplying gas of the branch midway of the pipe arrangement 6 of supplying gas 0), and it is delivered to treatment facility A as being used for unstripped gas organic substance is degraded and that be converted to geseous fuel/liquid fuel.
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), it is imported shift-converter 8 carry 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 are as described in the degraded method of the organic substance of the application first invention of front.Therefore, the waste gas (g that utilizes metallurgical furnace to produce 0), can improve carbon monoxide concentration by at least a portion of contained nitrogen is separated (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 rather than that produce off and on, also as describing 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 that produces continuously produces, in the situation that have flare stack in this waste gas system, the effect due to identical with the application's the second invention also can reduce the burning amount of diffusing.
On the other hand, in the situation that do not have the waste gas that the metallurgical furnace of the continuous generation of flare stack produces in the waste gas system, do not have the effect of the direct minimizing burning amount of diffusing.But geseous fuel, the liquid fuel by method manufacturing of the present invention is the fuel that can stably consume in the metal melting equipment of iron work etc., and has the high feature such as the combustion heat of comparing installation for blast furnace gas.Its result is, improved the energy efficiency of metal melting equipment integral body, as its result, reduced the external fuel amounts of buying such as Sweet natural gas or heavy oil, 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 gas-holder that temporarily stores converter gas, take-off pipe is set, can discharge section converter gas by 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 the liquid fuel trap generate the gas cooling gas cooler successively in the downstream side of this take-off pipe.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, be provided with thief hatch and under meter on the exit side pipe arrangement of the cooling rear gas of the exit side pipe arrangement of shift-converter and gas cooler.
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 3The pressure that/h supplies with as water vapour is 10kg/cm 2The steam of G is warming up to 320 ℃ with preheater, then it is 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 of 7 volume % (transformationreation generation gas).The flow that this transformationreation generates gas is 172Nm 3/ h (mass rate is 170kg/h), reactor outlet gas temperature are 430 ℃.
External heat type rotary furnace as the modified-reaction device is heated to 500 ℃ in advance, import transformationreation to this modified-reaction device and generate gas, simultaneously supply with 880kg/h the polyethylene that the break process as the model substance of plastic waste granulates, make it be warming up to 800 ℃ of plan temperature of reaction.After reaching 800 ℃, discharge the liquid resultant that is captured by the 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 that is captured by the liquid fuel trap, in addition, obtain LHV for geseous fuel.These be the results are shown in table 1.
Owing to generating gas as the transformationreation of raw material supplying 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 the unreacted amount of polyethylene, therefore, if geseous fuel (380kg/h) and liquid fuel (650kg/h) are defined as polyethylene decomposition rate with respect to the total yield that the transformationreation of supplying with generates gas and poly total amount (1050kg/h), in this example 1, polyethylene decomposition rate is 98%, is abundant high value, and is basically unconfirmed to generating the above hydrocarbon of C25, 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 simultaneously water vapour upgrading, carbonic acid gas upgrading, hydrogenation, these four reactions of hydrocracking.The LHV of the geseous fuel that generates is 8.9Mcal/Nm 3, heat increases to converter gas (1.9Mcal/Nm 3) 4.7 times.
[table 1]
Figure BDA00003001869000191
* 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 ℃ and 500 ℃ of these two levels with the 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 water vapor concentration and the vaporization rate of poly modification (temperature of reaction: 800 ℃) and the relation between liquefied fraction that transformationreation generates gas.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 the transformationreation of supplying with, 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 is that transformationreation generates the water vapor concentration of gas and by the relation between poly modification (temperature of reaction: the 800 ℃) geseous fuel that obtains and the LHV of liquid fuel.Wherein, the LHV of liquid fuel represents with the LHV of the every volume under the standard state of the gas conversion of liquid fuel.Shown in Fig. 6 is that transformationreation generates the water vapor concentration of gas and by the relation between PE modified polyethylene decomposition rate, particularly is illustrated in 500 ℃ of temperature of reaction identical with 800 ℃ of lower polyethylene decomposition rates.Shown in Fig. 7 be transformationreation generate the gas concentration lwevel of gas and the hydrogen concentration of the geseous fuel that obtains by PE modified (temperature of reaction: 800 ℃) between relation.Shown in Fig. 8 be transformationreation generate the hydrogen concentration of gas and the gas concentration lwevel of the geseous fuel that obtains by PE modified (temperature of reaction: 500 ℃) between relation.
Example 11
Fig. 9 illustrates the overview of the equipment that uses in this embodiment.This equipment possesses the vertical modified-reaction device 9 that has gas dispersion plate 90 in the bottom (internal volume: about 3m 3), in this modified-reaction device 9, fill to orlop the polyethylene a that the 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 that is generated by shift-converter 8 generates the bottom that gas is fed to modified-reaction device 9, sees through gas dispersion plate 90 and supplies in reactor, rises in reactor.The 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.Need to prove, 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 750 ℃, in addition, set the condition identical with example 1 (the 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 the growing amount of geseous fuel composition, liquid resultant and composition etc. 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 the temperature (namely 750 ℃) of hanging down 50 ℃ than example 1 is the effect of adding catalyzer.
[table 3]
Figure BDA00003001869000221
* 1 transformationreation generates gas+polyethylene
Example 12
Waste gas as the metallurgical furnace that contains carbon monoxide produces 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 by the PSA method of the following stated and separate, improved the concentration of carbon monoxide.
In the nitrogen that utilizes the PSA method separates, 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 supplies 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 of 7 volume % (transformationreation generation gas).
The flow that this transformationreation generates gas is 130Nm 3/ h (mass rate is 146kg/h), reactor outlet gas temperature are 430 ℃.Except using this transformationreation generate gas and the modified-reaction temperature is made as 600 ℃, similarly carried out PE modified reaction with example 1.Reaction result is: the 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, the LHV due to installation for blast furnace gas is 770kcal/Nm 3Therefore, can obtain the gas of the combustion heat more than 9 times.
Comparative example 1
For to utilize water vapour and hydrogen concentration all the PE modified reaction efficiency of low gas study, made consisting of H 2: 1 volume %, CO:61 volume %, CO 2: 19 volume %, H 2O:1 volume %, N 2: the standard gas of 18 volume %, utilize this gas to carry out PE modified reaction experiment.Its result is, at 800 ℃ 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 with is connected in the steel processed factory that connects two converter 1a, 1b carrying out diverse blowing on a flare stack that carries out diffusion combustion, 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 produce and continue 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 produce and continue 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.
During the horizontal exceeding 95% of gas-holder, T-valve begins diffusion combustion towards the flare stack side, then, is 92% when following in the level of gas-holder, finishes diffusion combustion.Shown in Figure 10 is to begin until change and the burning amount of diffusing (instantaneous delivery) through the gas-holder level after 6 hours from certain time.According to Figure 10, because during this period the accumulative total burning amount of diffusing is 4.7 ten thousand Nm 3/ hr, so the time average burning amount of diffusing is 7700Nm 3/ hr is with the ratio of time average exhausted air quantity, be that the diffusion combustion rate has reached 10%.
On the gaseous emission pipe arrangement of the gas-holder that temporarily stores converter gas, take-off pipe is set, makes and to pass through this take-off pipe discharge unit converter gas.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 the liquid fuel trap generate the gas cooling gas cooler successively in the downstream side of this take-off pipe.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 cooling rear gas of the exit side pipe arrangement of shift-converter and 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 after being warming up to 320 ℃ by preheater, imports to it 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 of 7 volume % (transformationreation generation gas).The flow that this transformationreation generates gas is 4130Nm 3/ h (mass rate is 4.1t/hr), reactor outlet gas temperature are 430 ℃.
External heat type rotary furnace as the modified-reaction device is heated to 500 ℃ in advance, import transformationreation generation gas in this modified-reaction device, simultaneously supply with 21t/hr the polyethylene that the break process as the model substance of plastic waste granulates, make it be warming up to 800 ℃ of plan temperature of reaction.After reaching 800 ℃, will be discharged by the liquid resultant that the liquid fuel trap captures, 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 that is captured by the liquid fuel trap, in addition, obtain LHV for geseous fuel.These be the results are shown in table 4.
Owing to generating gas as the transformationreation of raw material supplying 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 the unreacted amount of polyethylene, therefore, if geseous fuel (9.05t/hr) and liquid fuel (15.65t/hr) are defined as polyethylene decomposition rate with respect to the total yield that the transformationreation of supplying with generates gas and poly total amount (25.1t/hr), in this example 1, polyethylene decomposition rate is 98%, is fully high value, the generation to the above hydrocarbon of C25 unconfirmed basically, 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 simultaneously water vapour upgrading, carbonic acid gas upgrading, hydrogenation, these four reactions of hydrocracking.The LHV of the geseous fuel that generates is 8.9Mcal/Nm 3, heat increases to converter gas (1.9Mcal/Nm 3) 4.7 times.
[table 4]
Figure BDA00003001869000251
* 1 transformationreation generates gas+polyethylene
Shown in Figure 11 be this shop test the time the gas-holder level change and the burning amount of diffusing, shown in Figure 12 is by the burn variation of the amount of diffusing of the accumulative total that Figure 10 (conventional example) and Figure 11 (inventive example) try to achieve.By Figure 11 and Figure 12 as can be known, 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, the 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 by the error that produces of time average of trying to achieve the burning amount of diffusing than the variation of short period.

Claims (12)

1. the degraded method of an organic substance, the method comprises:
By the waste gas (g that contains carbon monoxide that produces in metallurgical furnace 0) in add excessive water vapour and make it carry out transformationreation, formation contains hydrogen that transformationreation generates and carbonic acid gas and the mixed gas (g) of the water vapour that do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, carry out the organic substance modification degraded.
2. the degraded method of organic substance according to claim 1, wherein, waste gas (g 0) be by the waste gas that contains carbon monoxide and nitrogen that produces from metallurgical furnace, at least a portion nitrogen being separated the waste gas that has improved carbon monoxide concentration.
3. the degraded method of organic substance according to claim 1 and 2, wherein, the water vapor concentration of mixed gas (g) is 5～70 volume %.
4. the degraded method of organic substance according to claim 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 described organic substance of any one according to claim 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. the manufacture method of a fuel, the method comprises:
The modifier of the organic substance that will obtain by the degraded method of the described organic substance of any one in claim 1～5 reclaims with the form of geseous fuel and/or liquid fuel.
The waste gas that produces of a metallurgical furnace utilize method, the method comprises:
Waste gas (the 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 the pipe arrangement and can not be stored in the waste gas (g of gas-holder of supplying gas that gas utilizes 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 and make it carry out transformationreation, formation contains hydrogen that transformationreation generates and carbonic acid gas and the mixed gas (g) of the water vapour that do not consume in transformationreation, this mixed gas (g) is contacted with organic substance, carry out the organic substance modification degraded.
The waste gas that produces of metallurgical furnace according to claim 7 utilize method, wherein, add excessive water vapour and make it carry out the waste gas (g of transformationreation 0) be by the waste gas that contains carbon monoxide and nitrogen that produces from metallurgical furnace, at least a portion nitrogen being separated the waste gas that has improved carbon monoxide concentration.
The waste gas that produces of according to claim 7 or 8 described metallurgical furnaces utilize method, wherein, the water vapor concentration of mixed gas (g) is 5～70 volume %.
The waste gas that produces of metallurgical furnace according to claim 9 utilize 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. the waste gas that according to claim 7～10, the described metallurgical furnace of any one produces 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.
12. the manufacture method of a fuel, the method comprises:
The modifier of the organic substance that will obtain by the described method of any one in claim 7～11 reclaims with the form of geseous fuel and/or liquid fuel.
CN201180047923.7A 2010-08-31 2011-08-30 Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace Active CN103154201B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2010-194553 2010-08-31
JP2010194553 2010-08-31
JP2010-266794 2010-11-30
JP2010266794 2010-11-30
JP2011-040992 2011-02-26
JP2011-040994 2011-02-26
JP2011040992 2011-02-26
JP2011040994 2011-02-26
PCT/JP2011/004812 WO2012029283A1 (en) 2010-08-31 2011-08-30 Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace

Publications (2)

Publication Number Publication Date
CN103154201A true CN103154201A (en) 2013-06-12
CN103154201B CN103154201B (en) 2014-11-05

Family

ID=45772408

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180047923.7A Active CN103154201B (en) 2010-08-31 2011-08-30 Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace

Country Status (3)

Country Link
JP (1) JP4968402B1 (en)
CN (1) CN103154201B (en)
WO (1) WO2012029283A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318433A (en) * 2015-06-18 2017-01-11 中国石油化工股份有限公司 Hydrotreatment method of animal and vegetable oil
CN108138058A (en) * 2015-10-07 2018-06-08 杰富意钢铁株式会社 The manufacturing method of the gasification process of carbonaceous fuel, the operating method of iron-smelter and gasifying gas
CN108350370A (en) * 2015-11-17 2018-07-31 杰富意钢铁株式会社 The manufacturing method of the gasification process of carbonaceous fuel, the operating method of iron-smelter and gasifying gas
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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6197266B2 (en) * 2012-03-27 2017-09-20 Ｊｆｅスチール株式会社 Method for producing modified coal
JP6227293B2 (en) * 2012-07-18 2017-11-08 Ｊｆｅスチール株式会社 Method for reducing the molecular weight of organic substances
JP6070580B2 (en) * 2014-01-14 2017-02-01 Ｊｆｅスチール株式会社 Method and system for reducing the molecular weight of organic substances
US20170247618A1 (en) 2014-07-31 2017-08-31 Jfe Steel Corporation Method of thermal decomposition of organic substance (as amended)

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
JPS62278769A (en) * 1986-05-27 1987-12-03 Nippon Kokan Kk <Nkk> Recovering method of co2 and h2 from converter gas
JPS62278770A (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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106318433A (en) * 2015-06-18 2017-01-11 中国石油化工股份有限公司 Hydrotreatment method of animal and vegetable oil
CN106318433B (en) * 2015-06-18 2018-09-28 中国石油化工股份有限公司 A kind of hydrotreating method of animal and plant fat
CN108138058A (en) * 2015-10-07 2018-06-08 杰富意钢铁株式会社 The manufacturing method of the gasification process of carbonaceous fuel, the operating method of iron-smelter and gasifying gas
CN108350370A (en) * 2015-11-17 2018-07-31 杰富意钢铁株式会社 The manufacturing method of the gasification process of carbonaceous fuel, the operating method of iron-smelter and gasifying gas
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

Also Published As

Publication number Publication date
WO2012029283A1 (en) 2012-03-08
JP2012188641A (en) 2012-10-04
CN103154201B (en) 2014-11-05
JP4968402B1 (en) 2012-07-04

Similar Documents

Publication Publication Date Title
CN103154201B (en) Method for decomposing organic substance into lower molecules, and method for utilizing exhaust gas generated by metallurgical furnace
CN104024148B (en) Method for preparing hydrogen
RU2600650C2 (en) Gas stream production
KR102298466B1 (en) Combined system for producing steel and method for operating the combined system
JP5835006B2 (en) Organic substance gasification method and organic substance gasification apparatus
KR102298465B1 (en) Method for generating synthesis gas in conjunction with a smelting works
US20160083810A1 (en) Blast furnace and method for operating a blast furnace
CN106795437A (en) Carbon dioxide produced by hydropyrolysis is used for the purposes of technique inerting
US20140343339A1 (en) Method for obtaining olefins from furnace gases of steel works
EP3311969A1 (en) Device for thermally decomposing polyethylene and polypropylene waste
KR20180109064A (en) Method for supplying hydrogen-containing reducing gas to the blast furnace shaft
CN1914117A (en) Hydrocarbon material processing system and method
US8198339B2 (en) Method for the production of fuels from waste
CN102482724A (en) Method for the simultaneous production of iron and crude syngas containing co and h2
EP3312223B1 (en) Method for thermally decomposing polyethylene and polypropylene waste
CN104136580B (en) The degraded method of organic substance
JP5835003B2 (en) How to make organic materials
US10890120B2 (en) Method for producing a fuel composition and for operating an internal combustion engine
JP5999115B2 (en) Method and system for reducing the molecular weight of organic substances
JP5906805B2 (en) How to operate a blast furnace or steelworks
CN1033267C (en) Synthesis gas production
JP6638661B2 (en) Organic substance pyrolysis method and pyrolysis equipment
LU102057B1 (en) Method for operating a blast furnace installation
JP6552030B1 (en) Syngas production system for low carbon FT synthetic oil production
Höftberger et al. In-situ CO2-adsorption in a dual fluidised bed biomass steam gasifier to produce a hydrogen rich gas

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant