CN109880653B - Preparation method and system of hydrogen-rich synthesis gas driven by residual heat of molten slag - Google Patents
Preparation method and system of hydrogen-rich synthesis gas driven by residual heat of molten slag Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention belongs to the technical field of waste heat recovery and utilization, and particularly relates to a system and a method for preparing hydrogen-rich synthesis gas driven by slag waste heat. The preparation system comprises a gasification reactor, a reforming reactor and a heat exchanger. The high-temperature slag is input into the gasification reactor through a high-temperature slag inlet, the slurry containing carbon solid fuel fine particles is input into the gasification reactor through a slurry inlet, and the water vapor is input into the gasification reactor through a water vapor inlet. The method comprises the steps of carrying out chemical reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles in a gasification reactor, inputting raw synthesis gas generated after the reaction into a reforming reactor, outputting synthesis gas containing hydrogen, carbon dioxide and steam after the reforming reaction, and then respectively removing the carbon dioxide and the steam to obtain the hydrogen-rich synthesis gas. The invention couples the technical advantages of the gasification reactor, the reforming reactor and the heat exchanger, not only effectively utilizes the high-quality waste heat and residual energy of the blast furnace slag, but also realizes the preparation of the hydrogen-rich synthesis gas.
Description
Technical Field
The invention belongs to the technical field of waste heat recovery and utilization, and particularly relates to a method and a system for preparing hydrogen-rich synthesis gas driven by slag waste heat.
Background
The iron and steel enterprises are energy-consuming households in China, and the waste heat resources of the iron and steel enterprises account for about one third of the fuel consumption. With the use of a series of technologies, the waste heat of iron and steel enterprises is recovered, but the sensible heat of blast furnace slag is not effectively recovered and utilized. Therefore, research on recycling of blast furnace slag waste heat has become a focus of attention in recent years. The blast furnace slag is produced in the blast furnace ironmaking process, the temperature discharged from the blast furnace is about 1500 ℃, the blast furnace slag is in a molten state, the enthalpy value of each ton of slag is about 1770MJ, and the enthalpy value is equivalent to the heat generated by the complete combustion of 60kg of standard coal. The blast furnace slag yield of China in 2018 reaches 2.5 hundred million tons, and the carried heat is equivalent to the calorific value of 1500 ten thousand tons of standard coal. The recycling of the blast furnace slag waste heat can effectively reduce the energy consumption of iron and steel enterprises, and is beneficial to realizing the aims of energy conservation and emission reduction.
The restriction factors of the recovery and utilization of the waste heat and the complementary energy of the blast furnace slag are mainly concentrated on three aspects: the blast furnace slag has low heat conductivity coefficient, and the requirement of a part of waste heat recovery equipment on the fluidity of the slag is high so as to achieve the optimal ratio of the slag flow to the air volume; the problems of energy consumption and pollution in the process of utilizing the waste heat of the blast furnace slag are serious, the traditional wet treatment mode has serious pollution to the environment, and the dry granulation method has higher requirements on the investment and the operation cost of the device; the subsequent utilization of cold slag is a considerable problem, the faster the cooling speed, the closer its properties are to the hydraulicity and strength of the cement material.
The current blast furnace slag treatment methods mainly comprise two types: water quenching and dry treatment. The water quenching method is that fresh water directly impacts the high-temperature slag to rapidly reduce the temperature of the high-temperature slag to form a large amount of glass state substances, the glass state substances are used as raw materials for producing cement, the produced hot water is only used for heating, bathing and the like in a factory area of a steel enterprise, and the waste heat recovery rate is only limited to about 10%. Typical water quenching processes are mainly the bottom filtration, the inbar process, the Tura process, the Lasa process and the so-called Teck process. The dry treatment method mainly comprises a mechanical crushing method, a wind quenching method and a centrifugal granulation method, and is used for recovering sensible heat of blast furnace slag, and because the methods have the problems of low heat recovery rate, unused latent heat, high energy consumption, difficult treatment and the like, the dry treatment method is still in an experimental research stage and is not widely applied to production practice.
The problem of recycling the residual heat and energy of the blast furnace slag is greatly valued, and research works are being carried out by iron and steel enterprises, colleges and universities and research institutes at home and abroad, but reports of wide industrial application of entity equipment are not seen so far, and mature technologies are not formed.
Disclosure of Invention
Technical problem to be solved
The invention provides a preparation method and a system of hydrogen-rich synthesis gas driven by slag waste heat, aiming at the technical problem of low recovery and utilization rate of blast furnace slag waste heat in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a hydrogen-rich synthesis gas preparation system driven by slag waste heat comprises a gasification reactor, a reforming reactor and a heat exchanger;
the gasification reactor is provided with a high-temperature slag inlet, a slurry inlet, a water vapor inlet, a slag outlet and a synthesis gas outlet, wherein the high-temperature slag is input into the gasification reactor through the high-temperature slag inlet, the slurry containing carbon solid fuel fine particles is input into the gasification reactor through the slurry inlet, and the water vapor is input into the gasification reactor through the water vapor inlet;
carrying out chemical reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles in a gasification reactor, inputting the crude synthesis gas generated after the reaction into a reforming reactor, inputting the slag into a heat exchanger, and preparing the steam by the heat exchanger through heat exchange with the slag;
the steam outlet of the heat exchanger is communicated with the steam inlets of the gasification reactor and the reforming reactor.
The hydrogen-rich synthesis gas preparation system also comprises a slag storage tank, a slurry storage of carbon-containing solid fuel fine particles, separation equipment, a collector, an absorption tower, a dryer, a hydrogen storage device and a blast furnace slag particle collector;
the slag storage tank is connected with the high-temperature slag inlet and is used for storing the high-temperature slag discharged by the blast furnace, so that the high-temperature slag can be stably and continuously output;
the slurry storage device for the carbon-containing solid fuel fine particles is connected with the slurry inlet, and is used for storing the prepared slurry for the carbon-containing solid fuel fine particles and providing reactants for gasification reaction in the gasification reactor;
a separation device is arranged between the gasification reactor and the reforming reactor, and can receive the crude synthesis gas which is mainly carbon monoxide and hydrogen and ash content and is generated by the gasification reactor, separate and output the crude synthesis gas and the ash content respectively, and input the separated crude synthesis gas into the reforming reactor;
the collector is connected with the ash outlet end of the separation equipment and is used for collecting the ash output by the separation equipment;
the absorption tower is connected with the gas outlet end of the reforming reactor and is used for receiving the synthesis gas containing hydrogen, carbon dioxide and water vapor output by the reforming reactor and absorbing the carbon dioxide therein to form the synthesis gas containing hydrogen and water vapor and output the synthesis gas;
the absorption tower is connected with a dryer, and the dryer is used for receiving the synthesis gas containing hydrogen and water vapor output by the absorption tower, absorbing the water vapor in the synthesis gas, forming hydrogen-rich synthesis gas and outputting the hydrogen-rich synthesis gas;
the hydrogen storage device is connected with the dryer and is used for receiving and storing the hydrogen-rich synthesis gas output by the dryer;
the blast furnace slag granulator is arranged between the heat exchanger and the gasification reactor and is used for receiving blast furnace slag discharged by the gasification reactor and forming high-temperature slag particles and outputting the high-temperature slag particles;
the heat exchanger is used for receiving high-temperature slag particles formed by the blast furnace slag granulator, generating steam in a heat exchange mode and outputting the steam to the gasification reactor and the reforming reactor;
the blast furnace slag particle collector is connected with the heat exchanger and is used for receiving slag particles discharged by the heat exchanger.
Preferably, the separation apparatus is a cyclone; the gasification reactor is a bubbling bed gasification reactor; the reforming reactor is a fixed bed reforming reactor; the heat exchanger is an indirect heat exchanger.
The preparation method of the hydrogen-rich synthetic gas driven by the residual heat of the molten slag adopts the hydrogen-rich synthetic gas preparation system driven by the residual heat of the molten slag to prepare the hydrogen-rich synthetic gas, and comprises the following steps:
s1: carrying out gasification reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles to generate crude synthesis gas mainly comprising carbon monoxide and hydrogen and ash;
s2: carrying out reforming reaction on the crude synthesis gas and steam to generate synthesis gas comprising hydrogen, carbon dioxide and steam;
s3: removing carbon dioxide from the synthesis gas generated in S2 to generate synthesis gas containing hydrogen and water vapor;
s4: removing water vapor in the generated synthesis gas containing hydrogen and water vapor to form hydrogen-rich synthesis gas;
the water vapor is prepared by using the heat of the slag generated by the reaction in the step S1, and the water vapor is provided for the reaction processes of S1 and S2.
The concentration of the slurry of carbonaceous solid fuel fine particles in step S1 is 50% to 60%.
Preferably, after step S1, a step of separating the raw syngas and the ash is further included.
Preferably, the gasification reaction temperature in step S1 is 1250 ℃ to 1450 ℃;
the reforming reaction temperature in step S2 is 350 ℃ to 650 ℃.
Preferably, the diameter of the carbonaceous solid fuel fine particles in the slurry of carbonaceous solid fuel fine particles in step S1 is 100 μm to 300 μm.
Preferably, the carbonaceous solid fuel fine particles in the slurry of carbonaceous solid fuel fine particles in step S1 include high-rank coal, medium-rank coal, low-rank coal, coal char, biomass, petroleum coke, oil shale, and/or carbonaceous solid waste.
Preferably, a reforming reaction catalyst is added in step S2, and the reforming reaction catalyst includes a supported metal catalyst;
the active component in the supported metal catalyst comprises a platinum, gold, silver, iron, molybdenum, copper or cobalt metal monomer or a composite supported metal catalyst formed by compounding any two or more of platinum, gold, silver, iron, molybdenum, copper and cobalt.
(III) advantageous effects
The invention has the beneficial effects that: according to the method and the system for preparing the hydrogen-rich synthetic gas driven by the residual heat of the slag, provided by the invention, the residual heat of the blast furnace slag is used for the gasification reaction of the solid fuel, particularly, the high-quality latent heat of the blast furnace slag is effectively utilized, and meanwhile, the water vapor used in the gasification reaction and the reforming reaction process is generated by the residual heat of the blast furnace slag, so that the energy consumption is reduced.
The preparation method disclosed by the invention couples the technical advantages of blast furnace slag waste heat utilization, solid fuel gasification reaction and reforming reaction, not only effectively utilizes the high-quality waste heat and waste energy of the blast furnace slag, but also realizes the preparation of the hydrogen-rich synthesis gas.
In conclusion, the preparation method provided by the invention realizes the preparation of the hydrogen-rich synthesis gas, utilizes the high-quality blast furnace slag waste heat, has the advantages of simple process flow, greatly reduced cost and energy consumption, no pollutant generation and important significance for energy conservation and consumption reduction of iron and steel enterprises.
Drawings
FIG. 1 is a schematic structural diagram of a slag waste heat-driven hydrogen-rich syngas production system according to an embodiment of the present invention;
[ description of reference ]
1: a slurry reservoir; 2: a slag storage tank; 3: a gasification reactor; 4: a cyclone separator; 5: a reforming reactor; 6: an absorption tower; 7: a dryer; 8: a hydrogen storage vessel; 9: a blast furnace slag granulator; 10: a heat exchanger; 11: an ash collector; 12: a blast furnace slag particle collector.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
As shown in fig. 1, the present embodiment provides a slag waste heat-driven hydrogen-rich synthesis gas production system, which includes a slurry storage 1 for fine particles of carbonaceous solid fuel, a slag storage tank 2, a gasification reactor 3, a cyclone 4, a reforming reactor 5, an absorption tower 6, a dryer 7, a hydrogen storage tank 8, a blast furnace slag granulator 9, a heat exchanger 10, an ash collector 11, and a blast furnace slag particle collector 12.
The slurry storage 1 for the fine particles of the carbonaceous solid fuel is connected with the gasification reactor 3 and is used for storing the prepared slurry of the fine particles of the carbonaceous solid fuel and providing reactants for the gasification reaction in the gasification reactor 3.
The slag storage tank 2 is connected with the gasification reactor 3 and is used for storing high-temperature slag discharged by the blast furnace, so that the high-temperature slag can be stably and continuously output.
The gasification reactor 3 is capable of chemically reacting a slurry of blast furnace slag, steam and fine particles of a carbonaceous solid fuel therein to produce a raw synthesis gas mainly comprising carbon monoxide and hydrogen, and an ash, and outputting the raw synthesis gas and the ash. The reactions that mainly take place in the gasification reactor 3 include:
disproportionation reaction:
and (3) oxidation reaction:
partial oxidation reaction:
water-gas reaction:
methanation reaction:
water-gas conversion reaction:
methane reforming reaction:
the cyclone 4, which is a separation device, is connected to the gasification reactor 3, and is capable of receiving the raw synthesis gas mainly containing carbon monoxide and hydrogen and the ash generated from the gasification reactor 3, separating the raw synthesis gas and the ash, and outputting the separated raw synthesis gas and ash.
An ash collector 11 is connected to the cyclone 4 for collecting the ash from the cyclone 4.
The reforming reactor 5 is connected with the separator 4, and is used for receiving the synthesis gas output by the cyclone separator 4, and enabling carbon monoxide in the synthesis gas and introduced steam to perform a water-gas shift reaction to generate hydrogen and carbon dioxide under the action of a catalyst at a certain temperature. The main reactions taking place in the reforming reactor include:
the absorption tower 6 is connected to the reforming reactor 5, and is configured to receive the synthesis gas mainly containing hydrogen, carbon dioxide and water vapor output from the reforming reactor 5, and absorb the carbon dioxide therein to form synthesis gas mainly containing hydrogen and water vapor, and output the synthesis gas. The main reactions taking place in the absorption column include:
the dryer 7 is connected with the absorption tower 6 and is used for receiving the synthesis gas mainly containing hydrogen and water vapor output by the absorption tower 6, absorbing the water vapor therein, forming hydrogen-rich synthesis gas and outputting the hydrogen-rich synthesis gas.
The hydrogen storage device 8 is connected with the dryer 7 and is used for receiving and storing the hydrogen-rich synthesis gas output by the dryer 7. From this, it can be understood that the production of the hydrogen-rich synthesis gas is carried out by the slurry storage 1 of the carbonaceous solid fuel fine particles, the slag storage tank 2, the gasification reactor 3, the cyclone 4, the reforming reactor 5, the absorption tower 6, the dryer 7, and the hydrogen storage 8.
The blast furnace slag granulator 9 is connected with the gasification reactor 3 and is used for receiving blast furnace slag discharged from the gasification reactor 3 after gasification reaction to form high-temperature slag granules and outputting the high-temperature slag granules, and the temperature of the blast furnace slag during the process is reduced to be below 1250 ℃, so that after the blast furnace slag granulator 9 is contacted with the slag, the temperature of the slag is continuously reduced to be below the solidifying point of the slag to form the blast furnace slag granules.
The heat exchanger 10 is connected with the blast furnace slag granulator 9 and is used for receiving high-temperature slag particles formed by the blast furnace slag granulator 9, generating steam in a heat exchange mode and outputting the steam to the gasification reactor 3 and the reforming reactor 5.
A blast furnace slag particle collector 12 is connected to the heat exchanger 10 for receiving slag particles discharged from the heat exchanger 10. Therefore, the recovery of the blast furnace slag residual heat and energy is realized by the slurry storage 1 of the carbon-containing solid fuel fine particles, the slag storage tank 2, the gasification reactor 3, the blast furnace slag granulator 9, the heat exchanger 10 and the blast furnace slag particle collector 12.
In summary, the preparation system of the embodiment utilizes the characteristics that the blast furnace slag contains a large amount of high-quality waste heat and the solid fuel gasification reaction needs heat supply, and innovatively provides a slag waste heat-driven hydrogen-rich synthesis gas preparation system. The gasification reactor 3 containing the blast furnace slag, the steam and the slurry of the carbon-containing solid fuel fine particles is designed, the high-quality waste heat of the blast furnace slag is effectively utilized to drive the gasification reaction, the heat exchanger 10 is additionally arranged, the residual heat of the blast furnace slag discharged by the gasification reactor 3 is utilized, and in addition, the reforming reactor 5 is arranged to convert the obtained crude synthesis gas into the hydrogen-rich synthesis gas. Therefore, the invention couples the technical advantages of the gasification reactor 3, the reforming reactor 5 and the heat exchanger 10, not only effectively utilizes the high-quality waste heat and residual energy of the blast furnace slag, but also realizes the preparation of the hydrogen-rich synthesis gas. In conclusion, the preparation system provided by the invention realizes the preparation of the hydrogen-rich synthesis gas, simultaneously utilizes the high-quality blast furnace slag waste heat, has the advantages of simple process flow, greatly reduced cost and energy consumption, no pollutant generation and important significance for energy conservation and consumption reduction of iron and steel enterprises.
With further reference to fig. 1, in this example the gasification reactor 3 is a bubbling bed gasification reactor. The top end of the gasification reactor 3 is provided with two fixed openings which are respectively connected with a slurry storage 1 and a slag storage tank 2 of carbon-containing solid fuel fine particles; meanwhile, the top end of the gasification reactor 3 is also provided with a crude synthesis gas outlet; the bottom end of the gasification reactor 3 is provided with two fixed openings, one fixed opening is used for introducing steam generated by the heat exchanger 10, the other fixed opening is used for discharging blast furnace slag with reduced temperature after reaction, the temperature of the blast furnace slag is reduced to below 1250 ℃, and the viscosity of the blast furnace slag is obviously increased compared with that before gasification reaction. In the process, blast furnace slag discharged from a blast furnace enters the slag storage tank 2 and is continuously introduced into the gasification reactor 3 at a stable flow rate, and when the amount of the blast furnace slag reaches a position of two thirds of the total capacity of the gasification reactor 3, the slurry of the carbon-containing solid fuel fine particles in the slurry storage 1 of the carbon-containing solid fuel fine particles and the steam generated by the heat exchanger 10 are simultaneously introduced. When the slurry containing the carbon solid fuel fine particles and the steam enter the gasification reactor 3, the temperature is rapidly increased to 1250-1450 ℃, the slurry containing the carbon solid fuel fine particles, the steam and the blast furnace slag are contacted with each other to generate a gasification reaction to generate a crude synthesis gas, the blast furnace slag continuously supplies heat for the gasification reaction along with the continuous addition of the slurry containing the carbon solid fuel fine particles, the steam and the blast furnace slag, and the gasification reaction is also rapidly carried out. The raw synthesis gas continuously produced in the process and the entrained ash enter the cyclone 4 through the gasification reactor 3 to separate the raw synthesis gas and the ash. Thus, it can be understood that the gasification reaction starts rapidly with the addition of slurry of fine particles of carbonaceous solid fuel and steam, high-quality sensible heat and latent heat of the blast furnace slag are converted into chemical heat of the gasification reaction, and the steam is bubbled as a gasifying agent when introduced from the bottom of the gasification reactor 3, thereby functioning as a stirring reaction zone and increasing the contact among reactants, the gasifying agent and the blast furnace slag.
Referring further to fig. 1, in the present embodiment, the slurry storage 1 for fine particles of carbonaceous solid fuel is not particularly limited, and only the related devices, which are technically mature, operationally and widely used, are required.
Referring further to fig. 1, in the present embodiment, the slag storage tank 2 is not particularly limited, and only needs to adopt related devices with mature technology, operation aspect and wide use. The selection of the slag storage tanks 2 is matched with the slag discharge of the blast furnace, the number of the slag storage tanks 2 arranged in the system is not limited to 1, a plurality of slag storage tanks can be adopted for storing blast furnace slag, the stable outflow of slag flow needs to be ensured in the use process of the slag storage tanks 2, the slag is prevented from blocking an outlet, and a certain anti-blocking device is required; meanwhile, because the temperature of blast furnace slag is high and the corrosion is strong, the adopted slag storage tank needs to have good heat preservation performance and corrosion resistance so as to ensure the smooth operation of the whole system.
With further reference to fig. 1, in this embodiment, the bottom of the gasification reactor 3 is provided with a fixed steam inlet, but the invention is not limited to the use of one inlet, but a plurality of evenly/unevenly distributed steam inlets may be used. The plurality of uniformly/unevenly distributed steam inlets are more favorable for the mutual contact of the slurry of the carbon-containing solid fuel fine particles, the steam and the blast furnace slag.
Referring further to fig. 1, in this embodiment, the present invention is not limited to the bubbling bed gasification reactor as the gasification reactor 3, and any reactor capable of simultaneously providing blast furnace slag, slurry of fine particles of carbonaceous solid fuel and steam may be used as the gasification reactor 3, and the inlet/outlet at each position is not limited to the position of the gasification reactor 3, and the inlet/outlet at each position may be different according to the structure of the gasification reactor, and it is sufficient to ensure that the introduction amount of blast furnace slag, slurry of fine particles of carbonaceous solid fuel and steam is matched during this process.
With further reference to fig. 1, in the present embodiment, cyclone 4 is connected to gasification reactor 3, reforming reactor 5 and ash collector 11. Specifically, an inlet is provided on a side wall surface of the cyclone 4, and the raw synthesis gas and the ash content enter the cyclone through the inlet; an outlet is arranged on the upper wall surface of the other side of the cyclone separator 4 and is used for discharging the synthesis gas which is treated by the cyclone separator 4 and does not contain ash; the bottom of the cyclone 4 is provided with an ash outlet for the discharge of ash. From the above, it can be understood that the raw synthesis gas containing synthesis gas and ash enters the cyclone from the gas inlet, and then the separated synthesis gas is discharged from the gas outlet, and the ash is discharged from the bottom outlet. The cyclone 4 of the present invention is not specially designed, and the size and the handling capacity of the cyclone 4 are matched with those of the gasification reactor 3.
Referring further to fig. 1, in the present embodiment, ash collector 11 is not particularly limited, and only requires the use of technically sophisticated, operationally and widely used associated equipment.
With further reference to FIG. 1, in this embodiment, the reforming reactor 5 is a fixed bed reactor, and the reforming reactor 5 is coupled to the cyclone 4 to receive the ash-depleted syngas. Specifically, the reforming reactor 5 is provided with a fixed gas inlet on one side wall surface to receive the ash-removed syngas, a fixed gas inlet on the other side wall surface to discharge the reformed syngas, and a fixed gas inlet on the bottom to receive the syngas generated by the heat exchanger 10. A supported metal catalyst is placed in the reforming reactor, wherein the active component mainly comprises a metal monomer such as platinum, gold, silver, iron, molybdenum, copper, cobalt and the like or a composite supported metal catalyst formed by compounding more than two of the metal monomers.
Referring further to fig. 1, in this embodiment, the present invention is not limited to the fixed bed reactor as the reforming reactor 5, any reforming reactor capable of performing the water gas shift reaction may be used as the reforming reactor 5, and the inlet/outlet of each position is not limited to the position of the reforming reactor 5, and the inlet/outlet of each position may be different according to the structure of the reforming reactor, in which process the carbon monoxide conversion efficiency is ensured to be high.
Referring further to fig. 1, in the present embodiment, the absorption tower 6 is connected to the reforming reactor 5, and is not particularly limited, and only the related devices, which are technically mature, operationally and widely used, are required. Specifically, the side wall surface of the absorption tower 6 is provided with a fixed gas inlet to receive the synthesis gas produced by the reforming reactor 5, the top center is provided with a spray device to absorb the carbon dioxide in the synthesis gas, and the other side surface of the absorption tower 6 is provided with a fixed gas outlet to discharge the synthesis gas from which the carbon dioxide gas is removed, wherein the synthesis gas mainly comprises hydrogen and water vapor.
Referring further to fig. 1, in the present embodiment, the dryer 7 is connected to the absorption tower 6, and there is no particular limitation, and only the related devices, which are technically mature, operationally and widely used, are required. Specifically, the side wall surface of the dryer 7 is provided with an air inlet and an air outlet to complete the drying of the synthesis gas, and the dried hydrogen-rich synthesis gas is discharged.
Referring further to fig. 1, in the present embodiment, the hydrogen storage device 8 is connected to the dryer 7, and there is no specific limitation, and only related devices that are technically mature, operationally and widely used are required.
With further reference to fig. 1, in this embodiment a blast furnace slag granulator 9 is connected to the gasification reactor 3 for forming blast furnace slag discharged from the gasification reactor into slag granules. Specifically, two oppositely-arranged rotary drums with opposite rotation directions are arranged in the blast furnace slag granulator, and blast furnace slag flows into the middle position of the two rotary drums after being discharged from the gasification reactor, is driven by the rotation of the rotary drums and is further cooled to form slag particles with solidified shells on the surfaces.
Referring further to fig. 1, in this embodiment, the blast furnace slag granulator 9 is not limited to the drum type of fig. 1, and any slag granulator capable of performing dry blast furnace slag granulation may be used as the blast furnace slag granulator 9, so as to ensure high granulation efficiency and uniform blast furnace slag granule size.
With further reference to fig. 1, in this embodiment, a heat exchanger 10 is connected to the blast furnace slag granulator 9 to recover residual heat and energy carried by the blast furnace slag granules discharged from the blast furnace slag granulator. Specifically, slag particles formed by the blast furnace slag granulator enter the heat exchanger 10, the side wall of the heat exchanger 10 is a water-cooled wall, and the high-temperature slag particles and cold water in the water-cooled wall indirectly exchange heat to form steam which is used in the gasification reactor 3 and the reforming reactor 5.
Referring to fig. 1, in this embodiment, the present invention is not limited to an indirect heat exchanger as the heat exchanger 10, any heat exchanger capable of effectively recovering the residual heat of the slag particles to form steam may be used as the heat exchanger 10, and the position of the water wall is not limited to the position of the heat exchanger 10, and may be different according to different heat exchanger structures, so that the heat exchange efficiency is ensured in the process.
Referring further to fig. 1, in the present embodiment, the blast furnace slag particle collector 12 is connected to the heat exchanger 10, and is not particularly limited, and only requires the use of a related apparatus which is technically mature, operationally and widely used.
In this embodiment, a method for preparing hydrogen-rich syngas driven by residual heat of slag is also provided, and in this embodiment, the preparation method can be implemented with reference to the preparation system. The method specifically comprises the following steps:
s1, carrying out gasification reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles to generate crude synthesis gas mainly comprising carbon monoxide and hydrogen and ash.
And S2, separating the formed crude synthesis gas from ash.
S3, introducing the crude synthesis gas into a reforming reactor to carry out reforming reaction with steam, wherein the generated gas mainly comprises hydrogen, carbon dioxide and steam.
S4, introducing the formed synthesis gas into an absorption tower to remove carbon dioxide, and generating the synthesis gas containing hydrogen and water vapor.
S5, introducing the generated synthesis gas containing hydrogen and water vapor into a drying tower to form hydrogen-rich synthesis gas.
And S6, forming steam by heat exchange of the blast furnace slag particles, and returning the steam to the steps S1 and S3 for use.
In summary, the preparation method of the embodiment utilizes the characteristics that the blast furnace slag contains a large amount of high-quality waste heat and the solid fuel gasification reaction needs heat supply, and innovatively provides a slag waste heat driven hydrogen-rich synthesis gas preparation method, which uses the waste heat of the blast furnace slag for the gasification reaction of the solid fuel, particularly effectively utilizes the high-quality latent heat of the blast furnace slag, and simultaneously generates steam used in the gasification reaction and the reforming reaction through the waste heat of the blast furnace slag, thereby reducing energy consumption. Therefore, the preparation method disclosed by the invention couples the technical advantages of the blast furnace slag waste heat utilization, the solid fuel gasification reaction and the reforming reaction, not only effectively utilizes the high-quality waste heat and waste energy of the blast furnace slag, but also realizes the preparation of the hydrogen-rich synthesis gas. In conclusion, the preparation method provided by the invention realizes the preparation of the hydrogen-rich synthesis gas, utilizes the high-quality blast furnace slag waste heat, has the advantages of simple process flow, greatly reduced cost and energy consumption, no pollutant generation and important significance for energy conservation and consumption reduction of iron and steel enterprises.
Further, in the present embodiment, the gasification reaction temperature in step S1 is 1250 ℃ to 1450 ℃; the reforming reaction temperature in step S2 is 350 ℃ to 650 ℃.
Further, in the present embodiment, the concentration of the slurry of fine carbonaceous solid fuel particles in step S1 is 50% to 60%.
Further, in the present embodiment, the diameter of the carbonaceous solid fuel fine particles in the slurry of carbonaceous solid fuel fine particles in step S1 is 100 μm to 300 μm.
Further, in the present embodiment, the fine carbonaceous solid fuel particles in the slurry of fine carbonaceous solid fuel particles in step S1 include high-rank coal, medium-rank coal, low-rank coal, coal char, biomass, petroleum coke, oil shale, and carbonaceous solid waste.
Further, in this embodiment, a reforming reaction catalyst is added in step S2, and the reforming reaction catalyst is mainly a supported metal catalyst, in which the active component is mainly a metal monomer such as platinum, gold, silver, iron, molybdenum, copper, and cobalt, or a composite supported metal catalyst formed by combining any two or more of them.
By adopting the preparation method and the preparation system, taking carbon-containing solid fuel coal dust as an example, the industrial analysis and the element analysis of the coal dust are shown in table 1, and the components and the concentrations of the components of the prepared hydrogen-rich synthesis gas are shown in table 2.
TABLE 1 Industrial and elemental analysis of coal dust
TABLE 2 composition and component concentrations of Hydrogen-enriched syngas
| Synthesis gas Components | H2 | CO | CO2 | CH4 |
| Component concentration (%) | 94.13 | 5.64 | 0.23 | - |
As can be seen from table 2, the method and the system for preparing hydrogen-rich syngas driven by slag waste heat provided in the above two embodiments not only achieve the preparation of hydrogen-rich syngas, the component concentration of which reaches 94.13%, but also effectively recycle the high-quality waste heat and residual energy of blast furnace slag.
Obviously, the production method of the present invention is not limited to the production system shown in example one as long as step S1 and step S3 can be completed. Meanwhile, it should be emphasized that although the preparation method is described by sequencing from S1 to S6, the sequence of the steps is not limited, and the sequence is not limited to the order listed in the above examples unless the subsequent steps must use the product of the previous step or the previous step is required to be performed as known to those skilled in the art.
The technical principles of the present invention have been described above in connection with specific embodiments, which are intended to explain the principles of the present invention and should not be construed as limiting the scope of the present invention in any way. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive efforts, which shall fall within the scope of the present invention.
Claims (8)
1. A hydrogen-rich synthesis gas preparation system driven by slag waste heat comprises a gasification reactor, a reforming reactor and a heat exchanger;
the gasification reactor is provided with a high-temperature slag inlet, a slurry inlet, a water vapor inlet, a slag outlet and a synthesis gas outlet, wherein the high-temperature slag is input into the gasification reactor through the high-temperature slag inlet, the slurry containing carbon solid fuel fine particles is input into the gasification reactor through the slurry inlet, and the water vapor is input into the gasification reactor through the water vapor inlet;
carrying out chemical reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles in a gasification reactor, inputting the crude synthesis gas generated after the reaction into a reforming reactor, inputting the slag into a heat exchanger, and preparing the steam by the heat exchanger through heat exchange with the slag;
the water vapor outlet of the heat exchanger is communicated with the water vapor inlets of the gasification reactor and the reforming reactor;
the hydrogen-rich synthesis gas preparation system also comprises a slag storage tank, a slurry storage of carbon-containing solid fuel fine particles, separation equipment, a collector, an absorption tower, a dryer, a hydrogen storage device and a blast furnace slag particle collector;
the slag storage tank is connected with the high-temperature slag inlet and is used for storing the high-temperature slag discharged by the blast furnace, so that the high-temperature slag can be stably and continuously output;
the slurry storage device for the carbon-containing solid fuel fine particles is connected with the slurry inlet, and is used for storing the prepared slurry for the carbon-containing solid fuel fine particles and providing reactants for gasification reaction in the gasification reactor;
a separation device is arranged between the gasification reactor and the reforming reactor, and can receive the crude synthesis gas which is mainly carbon monoxide and hydrogen and ash content and is generated by the gasification reactor, separate and output the crude synthesis gas and the ash content respectively, and input the separated crude synthesis gas into the reforming reactor;
the collector is connected with the ash outlet end of the separation equipment and is used for collecting the ash output by the separation equipment;
the absorption tower is connected with the gas outlet end of the reforming reactor and is used for receiving the synthesis gas containing hydrogen, carbon dioxide and water vapor output by the reforming reactor and absorbing the carbon dioxide therein to form the synthesis gas containing hydrogen and water vapor and output the synthesis gas;
the absorption tower is connected with a dryer, and the dryer is used for receiving the synthesis gas containing hydrogen and water vapor output by the absorption tower, absorbing the water vapor in the synthesis gas, forming hydrogen-rich synthesis gas and outputting the hydrogen-rich synthesis gas;
the hydrogen storage device is connected with the dryer and is used for receiving and storing the hydrogen-rich synthesis gas output by the dryer;
the blast furnace slag granulator is arranged between the heat exchanger and the gasification reactor and is used for receiving blast furnace slag discharged by the gasification reactor and forming high-temperature slag particles and outputting the high-temperature slag particles;
the heat exchanger is used for receiving high-temperature slag particles formed by the blast furnace slag granulator, generating steam in a heat exchange mode and outputting the steam to the gasification reactor and the reforming reactor;
the blast furnace slag particle collector is connected with the heat exchanger and is used for receiving slag particles discharged by the heat exchanger.
2. The slag waste heat-driven hydrogen-rich syngas production system of claim 1, wherein:
the separation equipment is a cyclone separator; the gasification reactor is a bubbling bed gasification reactor; the reforming reactor is a fixed bed reforming reactor; the heat exchanger is an indirect heat exchanger.
3. A slag waste heat-driven hydrogen-rich synthesis gas preparation method for preparing hydrogen-rich synthesis gas by using the slag waste heat-driven hydrogen-rich synthesis gas preparation system according to any one of claims 1-2, comprising the following steps:
s1: carrying out gasification reaction on blast furnace slag, steam and slurry of carbon-containing solid fuel fine particles to generate crude synthesis gas mainly comprising carbon monoxide and hydrogen and ash;
s2: carrying out reforming reaction on the crude synthesis gas and steam to generate synthesis gas comprising hydrogen, carbon dioxide and steam;
s3: removing carbon dioxide from the synthesis gas generated in S2 to generate synthesis gas containing hydrogen and water vapor;
s4: removing water vapor in the generated synthesis gas containing hydrogen and water vapor to form hydrogen-rich synthesis gas;
preparing water vapor by using the heat of the slag generated in the reaction in the step S1, and providing the required water vapor for the reaction processes of S1 and S2;
the concentration of the slurry of carbonaceous solid fuel fine particles in step S1 is 50% to 60%.
4. The slag waste heat-driven hydrogen-rich synthesis gas preparation method according to claim 3, characterized in that:
after step S1, a step of separating the raw syngas and the ash is also included.
5. The slag waste heat-driven hydrogen-rich synthesis gas preparation method according to claim 3, characterized in that:
the gasification reaction temperature in the step S1 is 1250-1450 ℃;
the reforming reaction temperature in step S2 is 350 ℃ to 650 ℃.
6. The slag waste heat-driven hydrogen-rich synthesis gas preparation method according to claim 3, characterized in that:
the diameter of the carbonaceous solid fuel fine particles in the slurry of carbonaceous solid fuel fine particles in step S1 is 100 μm to 300 μm.
7. The slag waste heat-driven hydrogen-rich synthesis gas preparation method according to claim 3, characterized in that:
the carbonaceous solid fuel fine particles in the slurry of carbonaceous solid fuel fine particles in step S1 include high-rank coal, medium-rank coal, low-rank coal, coal char, biomass, petroleum coke, oil shale, and/or carbonaceous solid waste.
8. The slag waste heat-driven hydrogen-rich synthesis gas preparation method according to claim 3, characterized in that:
a reforming reaction catalyst is added in the step S2, and the reforming reaction catalyst comprises a supported metal catalyst;
the active component in the supported metal catalyst comprises a platinum, gold, silver, iron, molybdenum, copper or cobalt metal monomer or a composite supported metal catalyst formed by compounding any two or more of platinum, gold, silver, iron, molybdenum, copper and cobalt.
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