CN106744683B - A kind of system preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil - Google Patents
A kind of system preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil Download PDFInfo
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- CN106744683B CN106744683B CN201611174545.XA CN201611174545A CN106744683B CN 106744683 B CN106744683 B CN 106744683B CN 201611174545 A CN201611174545 A CN 201611174545A CN 106744683 B CN106744683 B CN 106744683B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00092—Tubes
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0872—Methods of cooling
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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Abstract
A kind of system preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil, belong to the system that catalyzing and reforming biologic oil prepares hydrogen-rich synthetic gas, solve the problems, such as that existing ferrum-based catalyst recapitalization biological oil prepares hydrogen-rich synthetic gas process and easily leads to catalyst inactivation, solve the problems, such as that current China's iron ore grade is not high simultaneously, to realize the high-valued of bio oil and iron ore simultaneously.The present invention includes preheating device, steam generator, reforming reactor, heating furnace, purifying column and aircooling cabinet.Present invention composition is simple, efficient, energy conservation, economy, Project Realization is strong, raw material is applied widely, the product added value for improving iron ore catalytic reforming bio oil technique, suitable for the higher value application of the biological oil product based on different kind organism matter and the grade lifting process of various iron ore of low ore grade.
Description
Technical field
The invention belongs to the systems that catalyzing and reforming biologic oil prepares hydrogen-rich synthetic gas, and in particular to a kind of to be urged using iron ore
Change the system that recapitalization biological oil prepares hydrogen-rich synthetic gas.
Background technique
Primary product of the bio oil as biomass pyrolysis liquefaction, have energy density is high, transport storage is convenient, be easy into
The advantages that one step processes and realizes extensive focus utilization.Catalyzing and reforming biologic oil hydrogen manufacturing is current bio oil higher value application
A kind of important channel.Catalyzing and reforming biologic oil hydrogen manufacturing improves biological Oil-splited gasization activity using catalyst, to substantially reduce
Gasification temperature is cracked, is that current more feasible bio oil utilizes means.Studying at present more mainly has using dolomite as generation
The carbonate natural crystal catalyst of table and using nickel as the transition-metal catalyst of representative.The ores class catalyst valence such as dolomite
Lattice are cheap, but catalytic reforming effect is not very significant.The activity of nickel-base catalyst is high, and bio oil gasification cracking effect is good, but makes
With at high cost and toxic, it is also easy to carbon distribution occur and nickel particles is grown up, lead to catalyst inactivation.In recent years ferrum-based catalyst (Fe,
Fe2O3、Fe3O4Deng) because its is cheap, nontoxic and has preferable catalysis biological oil-breaking gasification and reformation hydrogen production effect, and by
Extensive concern.It is catalyst using the higher iron ore of iron-content, equally bio oil can be effectively converted, but iron ore exists
Carbon deposition quantity can still face the carbon distribution deactivation prob that other catalyst encounter, although can pass through burning up to 4% during being somebody's turn to do
Mode carries out catalyst regeneration, but easily causes sintering of catalyst in this way, destroys internal structure, reduces Adsorption, thus
Reduce the catalytic capability of catalyst.Therefore, seek one solve or be the task of top priority using the approach of iron ore carbon distribution.
China's iron and steel output ranks first in the world for years, but due to China be more than the iron content of 90% iron ore all
30% hereinafter, therefore needing import largely high-quality iron ore every year, the iron content of iron ore is improved as far as possible and reduces smelting
The consumption of coke has a very important significance the economic benefit for improving Iron and Steel Enterprises in China in the process.Made in steel industry
In natural iron ore, the bloodstone formed after dehydration has central hole structure, and specific surface area is up to 70m2/ g, pore structure ratio
It is more developed, have the potential quality as biological Oil-splited gas reforming catalyst.If iron ore is applied to catalyzing and reforming biologic oil
On the one hand gasification produces hydrogen-rich synthetic gas by bio oil catalytic pyrolysis and steam reforming, improve gaseous product quality；
On the other hand, the reducing atmosphere of the process is conducive to the reduction of ferriferous oxide in iron ore, improves iron content；Bio oil simultaneously
It is not oxidized that carbon distribution in reforming process in the formation of iron ore surface can protect iron ore, and reduces in subsequent ironmaking processes
The consumption of coke improves the grade of iron ore, so can be realized simultaneously high-qualityization of bio oil and iron ore, improves bio oil
The added value of catalytic reformate.
Summary of the invention
The present invention provides a kind of system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil, solves existing iron
Base catalyst recapitalization biological oil prepares the problem of hydrogen-rich synthetic gas process easily leads to catalyst inactivation, while solving current China's iron
The not high problem of the grade of ore, to realize the high-valued of bio oil and iron ore simultaneously.
A kind of system preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil provided by the present invention, including it is pre-
Thermal, steam generator, reforming reactor, heating furnace, purifying column and aircooling cabinet, it is characterised in that:
Bio oil is sent into reforming reactor after preheating via preheating device, vapor is sent into and is reformed by the steam generator
Reactor, iron ore and calcium oxide are sent into reforming reactor via charging gear respectively, and the heating furnace generates high-temperature flue gas and is
Reforming reactor provides heat；
Bio oil and iron ore, vapor, calcium oxide carry out catalytic reforming reaction in reforming reactor, generate thick hydrogen-rich
Synthesis gas, while generating high temperature plating carbon iron ore；
The thick hydrogen-rich synthetic gas is sent into purifying column, and condensation cleaning goes moisture removal and other impurities to obtain hydrogen-rich synthetic gas；
The high temperature plating carbon iron ore, which enters, is cooled to environment temperature in aircooling cabinet, obtain high grade iron ore.
The system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil, it is characterised in that:
The reforming reactor is the both ends sealed cylinder constituted by inside and outside two layers, the space that internal layer surrounds be bio oil with
The annulus of the reforming reaction region of iron ore, vapor, calcium oxide, outer layer and interior interlayer is used to introduce heating furnace generation
High-temperature flue gas provides heat for the reforming reaction in internal layer；
The heating furnace is industrial oil fired boiler, and it is that fuel generates high-temperature flue gas feeding reforming reactor that bio oil, which can be used,
The annulus of outer layer and interior interlayer；The high-temperature flue gas waste heat that the heating furnace generates can be used for steam generator and pre- hot charging
It sets, realizes UTILIZATION OF VESIDUAL HEAT IN.
The system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil, it is characterised in that:
The purifying column is packed tower, and thick hydrogen-rich synthetic gas removes moisture therein and other by the packing area of packed tower
Impurity obtains clean hydrogen-rich synthetic gas；
Tube bundle heat exchanger is used in the aircooling cabinet, air is passed through in tube bank, is restrained outer high temperature of placing and is plated carbon iron
Ore, the hot-air after heat exchange in tube bank burn for heating furnace, realize that energy regenerating utilizes.
When preparing hydrogen-rich synthetic gas using catalytic reforming bio oil of the present invention, the object of reforming reaction is participated in reforming reactor
Expect mass ratio are as follows: with bio oil for 1, vapor is 0.3~2, and iron ore is 0.5~2, and calcium oxide is 0.5~3；Reforming reaction
Temperature control is at 650 DEG C~850 DEG C in device.
Compared with prior art, the present invention has the advantages that
1, the present invention it is comprehensive solve the problems, such as bio oil it is high-valued in catalyst and iron ore grade is not generally high asks
Topic, to catalyzing and reforming biologic oil, produces hydrogen-rich synthetic gas using iron ore, meanwhile, iron ore is partially reduced and surface plating
Carbon, without considering that the carbon distribution deactivation prob of iron ore, the carbon distribution on opposite iron ore surface can also promote its grade, reduce subsequent refining
Coke ratio during iron, to achieve the purpose that obtain two kinds of high-value products.
2, in technique of the invention during iron ore catalytic reforming bio oil produces hydrogen-rich gas and meanwhile be added oxygen
Change calcium, can not only produce hydrogen process to biological Oil-splited gasization and play catalytic action, can also be captured in reforming process by situ
CO2And strengthen hydrogen production process, to play the dual promotion of iron ore and calcium oxide to catalyzing and reforming biologic oil hydrogen manufacturing simultaneously
The purpose for strengthening hydrogen manufacturing is realized in effect.
3, be used as in technique of the invention catalyzing and reforming biologic oil produce hydrogen-rich synthetic gas iron ore and calcium oxide weight
It is not required to be separated after whole reaction, contained calcium oxide can remove silica etc. in iron ore as flux in ironmaking processes
Impurity.
4, the hot-air in aircooling cabinet is used as to the burning oxygen of biological oil firing in heating furnace in technique of the invention
Agent has recycled partial heat, reduces system energy consumption.
5, the high-temperature flue gas that heating furnace generates in technique of the invention provides heat purpose for reforming reactor realizing
Afterwards, fume afterheat can be used for steam generator and biological oil heating unit, realize waste heat recycling.
6, the target product of technique of the invention can be by adjusting bio oil delivery rate, iron ore delivery rate, water
The conditions such as steam delivery rate, calcium oxide delivery rate, reforming reactor temperature, carry out the product of two kinds of target products of optimising and adjustment
Matter, technological applicability is strong and applicability is wide, and scale is easily controllable.
In short, the present invention by utilizing iron ore catalytic reforming bio oil, while producing hydrogen-rich synthetic gas, and obtains
The iron ore that grade gets a promotion is a kind of effective system of two kinds of high-quality products of coproduction simultaneously.The present invention is compared to life
Raw material of substance energy density is high, is easier to the bio oil of storage transport as the raw material for producing hydrogen-rich synthetic gas, more conducively industry
Large-scale application, and be conducive to the higher value application of bio oil.On the other hand using biological oil reforming in the process in iron ore table
The carbon distribution that face generates, reduces the coke-iron-rate of subsequent ironmaking, improves the grade of iron ore, tool energy-saving for steel industry
There is important meaning.Present invention composition is simple, efficient, energy conservation, economy, Project Realization is strong, raw material is applied widely, improves
The product added value of iron ore catalytic reforming bio oil technique, suitable for the high-valued of the biological oil product based on different kind organism matter
Using and various iron ore of low ore grade grade lifting process.
Detailed description of the invention
Fig. 1 is composed structure schematic diagram of the invention.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and embodiments.
As shown in Figure 1, the present invention includes preheating device, steam generator, reforming reactor, heating furnace, purifying column and sky
Air cooling room；
Bio oil is sent into reforming reactor after preheating via preheating device, vapor is sent into and is reformed by the steam generator
Reactor, iron ore and calcium oxide are sent into reforming reactor via charging gear respectively, and the heating furnace generates high-temperature flue gas and is
Reforming reactor provides heat；
Bio oil and iron ore, vapor, calcium oxide carry out catalytic reforming reaction in reforming reactor, generate thick hydrogen-rich
Synthesis gas, while generating high temperature plating carbon iron ore；
The thick hydrogen-rich synthetic gas is sent into purifying column, and condensation cleaning goes moisture removal and other impurities to obtain hydrogen-rich synthetic gas；
The high temperature plating carbon iron ore, which enters, is cooled to environment temperature in aircooling cabinet, obtain high grade iron ore.
As one embodiment, shell-and-tube heat exchanger is respectively adopted in preheating device and steam generator；Reforming reactor is adopted
The both ends sealed cylinder constituted with inside and outside two layers, the space that internal layer surrounds are the weight of bio oil and iron ore, vapor, calcium oxide
The high-temperature flue gas that the annulus of whole conversion zone, outer layer and interior interlayer is used to introduce heating furnace generation is anti-for the reformation in internal layer
Heat should be provided；Heating furnace uses common industrial oil fired boiler；Purifying column is using the common packed tower of industry；Aircooling cabinet
Using tube bundle heat exchanger, it is passed through air in tube bank, places high temperature in the confined space of tube bank and plates carbon iron ore.
Bio oil and iron ore, vapor, calcium oxide carry out catalytic reforming reaction in reforming reactor, participate in reforming anti-
The quality of material ratio answered are as follows: with bio oil for 1, vapor is 0.3~2, and iron ore is 0.5~2, and calcium oxide is 0.5~3；
Temperature control is at 650 DEG C~850 DEG C in reforming reactor.
Claims (3)
1. a kind of system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil, including preheating device, steam generation
Device, reforming reactor, heating furnace, purifying column and aircooling cabinet；It is characterized by:
Bio oil is divided into two-way after preheating via preheating device, be sent into reforming reactor all the way, and another way is sent into heating furnace；It is described
Vapor is sent into reforming reactor by steam generator, and iron ore and calcium oxide are sent into reforming reaction via charging gear respectively
Device, the heating furnace generate high-temperature flue gas and provide heat for reforming reactor；In reforming reactor temperature control 650 DEG C~
850℃；
Bio oil and iron ore, vapor, calcium oxide carry out catalytic reforming reaction in reforming reactor, generate thick hydrogen-rich synthesis
Gas, while generating high temperature plating carbon iron ore；
The thick hydrogen-rich synthetic gas is sent into purifying column, and condensation cleaning goes moisture removal and other impurities to obtain hydrogen-rich synthetic gas；It is described
High temperature plating carbon iron ore, which enters, is cooled to environment temperature in aircooling cabinet, obtain high grade iron ore.
2. the system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil as described in claim 1, feature exist
In:
The reforming reactor is the both ends sealed cylinder constituted by inside and outside two layers, and the space that internal layer surrounds is bio oil and iron ore
The annulus of the reforming reaction region of stone, vapor, calcium oxide, outer layer and interior interlayer is used to introduce the high temperature of heating furnace generation
Flue gas provides heat for the reforming reaction in internal layer；
The heating furnace be industrial oil fired boiler, use bio oil be fuel generate high-temperature flue gas be sent into reforming reactor outer layer and
The annulus of interior interlayer；The high-temperature flue gas waste heat that the heating furnace generates is used for steam generator and preheating device, more than realization
Heat utilization.
3. the system for preparing hydrogen-rich synthetic gas using iron ore catalytic reforming bio oil as claimed in claim 1 or 2, feature
It is:
The purifying column is packed tower, and thick hydrogen-rich synthetic gas removes moisture therein by the packing area of packed tower and other are miscellaneous
Matter obtains clean hydrogen-rich synthetic gas；
Tube bundle heat exchanger is used in the aircooling cabinet, air is passed through in tube bank, is restrained outer high temperature of placing and is plated carbon iron ore,
Hot-air after heat exchange in tube bank burns for heating furnace, realizes that energy regenerating utilizes.
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Citations (4)
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|---|---|---|---|---|
| CN101177239A (en) * | 2007-10-15 | 2008-05-14 | 中国科学技术大学 | Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil |
| CN101475143A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Biomass hydrogen production in water vapour atmosphere and series fluidized bed apparatus system thereof |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN104477847A (en) * | 2014-12-02 | 2015-04-01 | 中山大学 | Method for producing hydrogen by reforming biological oil by virtue of plasma |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177239A (en) * | 2007-10-15 | 2008-05-14 | 中国科学技术大学 | Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil |
| CN101475143A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Biomass hydrogen production in water vapour atmosphere and series fluidized bed apparatus system thereof |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN104477847A (en) * | 2014-12-02 | 2015-04-01 | 中山大学 | Method for producing hydrogen by reforming biological oil by virtue of plasma |
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