CN101638590B - Method for producing synthesis gas by combustible solid waste chemical chain gasification and interconnected fluidized bed reactor - Google Patents

Method for producing synthesis gas by combustible solid waste chemical chain gasification and interconnected fluidized bed reactor Download PDF

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Publication number
CN101638590B
CN101638590B CN 200910042076 CN200910042076A CN101638590B CN 101638590 B CN101638590 B CN 101638590B CN 200910042076 CN200910042076 CN 200910042076 CN 200910042076 A CN200910042076 A CN 200910042076A CN 101638590 B CN101638590 B CN 101638590B
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bed
fluidized bed
solid waste
oxygen
reactor
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CN 200910042076
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Chinese (zh)
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CN101638590A (en
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何方
李海滨
赵增立
陈勇
李常河
王小波
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中国科学院广州能源研究所
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/16Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]

Abstract

The invention provides a method for producing synthesis gas by combustible solid waste chemical chain gasification and an interconnected fluidized bed reactor. The method is implemented in an interconnected fluidized bed reactor, and the interconnected fluidized bed reactor comprises a fuel reactor and an air reactor communicated with each other internally. The combustible solid waste produces gasification reaction with a carrier of oxygen to produce synthesis gas, and the oxygen element necessary for the gasification of combustible solid waste comes from the lattice oxygen in the carrier component of oxygen; the carrier of oxygen without lattice oxygen is transported to the air reactor, in the air reactor, the carrier of oxygen is re-oxidized by high-temperature air to recovery to lattice oxygen; the carrier of oxygen recovered with lattice oxygen is carried out the air reactor by high-speed air, returns back to the fuel reactor for cycle use and produces gasification reaction with the combustible solid waste again. The invention relates to a high-efficiency combustible solid waste gasification technique breaking the prior art, and the invention can produce high-quality synthesis gas and reduce the contents of tar and carbon deposite during the gasification process.

Description

A kind of method of producing synthesis gas by combustible solid waste chemical chain gasification and interconnected fluidized bed reactor

Technical field

The present invention relates to new forms of energy and field of renewable energy technology, relate in particular to a kind of method and interconnected fluidized bed reactor of producing synthesis gas by combustible solid waste chemical chain gasification.

Technical background

Because reducing day by day and problem of environmental pollution that fossil energy utilizes process to bring of fossil oil, the renewable energy source of research, development and utilization cleaning has become working energy person's important subject.At present, China clears 1.5 hundred million tons of domestic wastes in annual agricultural crop straw 8.4 hundred million ton, years that produce, and this wherein has sizable ratio is the flammable solid waste that can be used as energy raw material.The flammable solid waste that comprises biomass resource has advantages such as stock number is big, renewable, environmental pollution is little, therefore, research and develop novel, flammable solid waste trans-utilization technology also becomes one of research focus of new energy field efficiently.Wherein, the flammable solid waste gasification is considered to more promising flammable solid waste transformation technology.In general fluidized bed gasification reactor, if expectation obtains high heating value or hydrogen-rich synthetic gas, then need provide oxygen rich gas or high-temperature vapor, thereby make technology become complicated, the gasification cost up as vaporized chemical.In addition; Traditional flammable solid waste gasification process also can produce a large amount of tar; Not only influence the overall gasification efficiency of flammable solid waste; Also can produce problems such as obstruction, corrosion to reactor drum and support equipment, these problems have also restricted the large-scale promotion and the utilization of flammable solid waste gasification technology.

At present; Though the report that gasifies in interconnected fluidized bed about biomass has on a small quantity been arranged; But in interconnected fluidized bed, the employing MOX is an oxygen carrier, through the chemical chain reaction mode process of flammable solid waste gasification preparing synthetic gas is also rarely reported.

Summary of the invention

An object of the present invention is to provide a kind of method of producing synthesis gas by combustible solid waste chemical chain gasification.

The interconnected fluidized bed reactor that another object of the present invention is to provide the method for said producing synthesis gas by combustible solid waste chemical chain gasification to use.

For achieving the above object, the present invention has taked following technical scheme:

Flammable solid waste chemical chain gasification of the present invention prepares the method for synthetic gas, it is characterized in that this method implements in a serial fluidized-bed reactor, and said interconnected fluidized bed reactor comprises the fuel reaction device and the air reactor of inner UNICOM; The fuel reaction device is a bubbling fluidized bed; Air reactor is a fluidized-bed riser tube, and this method may further comprise the steps:

1) with flammable solid waste raw material pulverize, subsequent use after the pre-treatment such as drying;

2) the flammable solid waste generates synthetic gas with oxygen carrier generating gasification reaction in the fuel reaction device, and the required oxygen element of flammable solid waste gasification is from the lattice oxygen in the oxygen carrier molecule;

3) lose oxygen carrier after the lattice oxygen, be transferred to air reactor, in air reactor, oxygen carrier is replied lattice oxygen by high temperature air oxidation again;

4) oxygen carrier after the answer lattice oxygen is taken out of air reactor by high-speed air, returns the fuel reaction device again and recycles, and reacts with flammable solid waste generating gasification once more.

The agent structure of the interconnected fluidized bed reactor that the inventive method is used comprises the fluidized-bed reactor of two inner UNICOMs, i.e. fuel reaction device and air reactor; The fuel reaction device is a bubbling fluidized bed, and feeding screw links to each other with the high-temperature zone of bubbling fluidized bed, and air distribution plate is arranged at the bottom of bubbling fluidized bed, and the aperture of fluidizing agent on air distribution plate upwards flows, and makes goods fluid; The middle part of bubbling fluidized bed is an expanding section, and expanding section is bigger than conversion zone bore, thereby gas flow rate is reduced, and prevents that material from being taken away by gas; Air reactor is a fluidized-bed riser tube; A revert pipe UNICOM is arranged between bubbling fluidized bed and fluidized-bed riser tube; Wind-distributing pipe is arranged at fluidized-bed riser tube bottom; Material reacts in high temperature air; And taken out of the fluidized-bed riser tube through the fluidized-bed riser tube by high-speed air, the material of taking out of returns bubbling fluidized bed after isolating chip and residue through cyclonic separator; The top of bubbling fluidized bed has a venting hole, and product gas flows out bubbling fluidized bed after cyclonic separator leads to gas-cleaning installation after isolating solid residue from venting hole.

The step of the inventive method further specifies as follows:

(1) with flammable solid waste raw material pulverize, subsequent use after the pre-treatment such as drying;

Said flammable solid waste raw material comprises agricultural crop straw, agricultural processing waste, domestic waste combustibleconstituents etc.

(2) oxygen carrier is formed by transition metal oxide, inert support and adhesive preparation; The oxygen carrier particle for preparing is seated in advance serves as bed material in the bubbling fluidized bed; Open the outer heating power supply of fluidized-bed; The bed material is preheating to assigned temperature, generally speaking, can and be stabilized in the 500-900 ℃ of scope the heating of bed material;

The transition metal oxide of said preparation oxygen carrier includes but not limited to NiO, CuO, Fe 2O 3, Mn 3O 4The inert support of said preparation oxygen carrier includes but not limited to Al 2O 3, SiO 2, MgO, NiAl 2O 4, MgAl 2O 4, ZrO 2The sticker of said preparation oxygen carrier includes but not limited to Al 2O 3, SiO 2, YSZ.

(3) adopt water vapour as fluidizing agent; Feed from bubbling fluidized bed bottom, make oxygen carrier realize fluidization, after temperature, a fluidisation of treating the bed material all stablized; Flammable solid waste raw material adds in the bed material in the bubbling fluidized bed through feeding screw; Flammable solid waste raw material is heated, and dewater rapidly in the back, reactions such as pyrolysis, gasification, and gaseous product, tar and fixed carbon continuation and oxygen carrier react, and solid waste is further gasified.Gasification product is derived by the bubbling fluidized bed top, further utilizes through purifying the back.The gaseous product component can be analyzed through the sampling of gas sampling mouth, according to analytical results, can further regulate operating parameterss such as gasification temperature, oxygen carrier/flammable solid waste ratio, water vapour addition and improve gaseous product distribution, gas heating value etc.;

(4) reacted oxygen carrier returns the fluidized-bed riser tube through the revert pipe that is installed in the bubbling fluidized bed middle part.In the fluidized-bed riser tube, the oxygen carrier that is in reduced state is oxidized to the state of oxidation again by the dioxygen oxidation in the high temperature air, replys its lattice oxygen.Oxygen carrier oxidation by air reaction is a strong exothermic reaction, usually, can the temperature of reaction in the air reactor be controlled in the 600-950 ℃ scope according to reaction conditions;

(5) product gas flows out bubbling fluidized bed after cyclonic separator leads to gas-cleaning installation after isolating solid residue from venting hole; Again the oxygen carrier particle after the oxidation is taken out of the fluidized-bed riser tube by high-speed air, after cyclonic separator is isolated the oxygen carrier chip of gasification reaction residue and breakage, returns in the fuel reaction device, and continuation and flammable solid waste react.

Bubbling fluidized bed is the fuel reaction device, and the fluidized-bed riser tube is an air reactor.In order to guarantee fuel reaction device and air reactor, can be respectively be equipped with external electrical heaters at the conversion zone of two reactor drums the carrying out smoothly of initial reaction stage.In addition, in order to prevent mutual convection current of gas and the leakage in fuel reaction device and the air reactor, at the revert pipe middle part sealing chamber is set, the oxygen carrier particle can be full of sealing chamber and plays sealing function in returning the air reactor process.

The producing synthesis gas by combustible solid waste chemical chain gasification method that the present invention proposes can solve a series of problems that traditional flammable solid waste gasification process is produced, and makes the flammable solid waste in the dual serial fluidized-bed reactor, be converted into the high-quality synthetic gas efficiently, economically.The present invention adopts transition metal oxide as the bed material in oxygen carrier and the fuel reaction device; The flammable solid waste reacts with oxygen carrier in the fuel reaction device and gasifies; The required oxygen element of gasification is mainly provided by the intramolecular lattice oxygen of oxygen carrier; And do not need extra additional oxygen-rich air as vaporized chemical, can reduce the gasification cost.Oxygen carrier after being reduced returns air reactor by air oxidation again, replys lattice oxygen, recycles through returning the fuel reaction device behind the cyclonic separator separation lime-ash then.If in the fuel reaction device, adopt water vapour as fluidizing agent, then gaseous product can obtain the synthetic gas of high heating value not by N2 and other inert gas dilutions.The oxygen carrier that with the transition metal oxide is main ingredient can also have catalysed oxidn to tar and the carbon distribution that produces in the gasification, can reduce the coal-tar middle oil generation with carbon distribution of gasification.

The present invention is a kind of waste gasification of flammable solid efficiently technology that has broken through prior art, can produce high-quality synthetic gas, and can reduce gasification tar, carbon distribution content.The present invention compared with prior art has the following advantages:

(1) adopts the lattice oxygen in the oxygen carrier molecule to originate, do not need pure oxygen or oxygen-rich air, only need small amount of water vapor, can reduce flammable solid waste gasification cost as fluidizing medium as vaporized chemical as the oxygen element of flammable solid waste gasification;

(2) owing to need not the vaporized chemical of oxygen-rich air as the flammable solid waste, then prepared synthetic gas is not by N 2The superfluous O of complete reaction not 2Dilute, improved the calorific value of synthetic gas;

(3) MOX in the oxygen carrier and metals ion can play katalysis to tar and the carbon distribution that flammable solid pyrolysis of waste process produces; So this gasification technology can reduce the tar and the carbon distribution productive rate of flammable solid waste gasification process, improve gasification efficiency;

(4) the oxygen carrier particle can not only play the oxygen carrier effect, can also play the thermal barrier effect simultaneously, brings the reaction heat of emitting in the air reactor into the fuel reaction device, has practiced thrift the energy; There is heat transfer, the mass transfer condition that has also improved in the fuel reaction device in the oxygen carrier particulate, helps flammable solid waste gasification successful reaction and carries out.

Description of drawings

Accompanying drawing 1 is interconnected fluidized bed reactor structural representation of the present invention.

Among the figure, 1-feeding screw, 2-bubbling fluidized bed (fuel reaction device), 3-revert pipe, 4-fluidized-bed riser tube (air reactor), 5-cyclonic separator, 6-cyclonic separator

Embodiment

Further specify the present invention below in conjunction with embodiment, but the present invention is not constituted restriction.

Choosing the agricultural processing waste is biomass material, median size 0.8mm; Fe 2O 3The quality percentage composition is that 60% ferric oxide particle is an oxygen carrier, and median size is 0.5mm; Bubbling fluidized bed 2 internal diameter 300mm, high 1200mm; Fluidized-bed riser tube 4 diameter 100mm, high 2000mm, initial oxygen carrier particle add-on is 30-40kg, can in bubbling fluidized bed 2, replenish fresh oxygen carrier at any time according to reaction process.Bubbling fluidized bed 2 temperature-stables are in 840-850 ℃ of scope, and fluidized-bed riser tube 4 temperature are controlled in 900-950 ℃, and the synthetic gas of producing is discharged by the vapor pipe at bubbling fluidized bed 2 tops and purified post analysis, utilization.

Implementation process is following: the biomass material that will be crushed to 0.8mm is placed in the loft drier, and is subsequent use at 90 ℃ times dry 24 hours; 35kg oxygen carrier particle is loaded in the bubbling fluidized bed 2, opens the outer heating power supply of bubbling fluidized bed 2 and fluidized-bed riser tube 4, the oxygen carrier bed material in the bubbling fluidized bed 2 is heated to 850 ℃; Open steam cock, water vapour is fed from bubbling fluidized bed 2 bottoms, the steam regulation flow velocity makes the bed material can reach the bubbling fluidized bed state; Open feeding screw 1; Biomass material is joined in the oxygen carrier material bed, and with oxygen carrier, water vapour reaction, it is 10-12kg/h that biomass add speed; Product gas is discharged through the venting hole at bubbling fluidized bed 2 tops; Isolate solid residue and the chip that gas is taken out of through cyclonic separator 6, purify the post-sampling analysis, further utilize then; Judge according to the product gas proximate analysis, when the lattice oxygen in the oxygen carrier soon reacts completely, open revert pipe 3; The oxygen carrier that reacts completely is brought into revert pipe 3 by gas, gets into air reactor, and oxygen carrier is by 950 ℃ high temperature air oxidation; Be returned to the primary state of oxidation, the oxygen carrier particle after oxidized is taken out of fluidized-bed riser tube 4 by high-speed air; Isolate chip and residue through cyclonic separator 5, return bubbling fluidized bed 2 again and recycle.

The present embodiment material composition is analyzed as shown in table 1:

Table 1 material composition analysis (unit: quality percentage composition %)

The present embodiment result of implementation is following:

Biomass consumption: 10-12kg/h

Average factor of created gase: 1.9m 3/ kg biomass

Gaseous product staple: H 238.2%, CO 15.7%, CO 223.5%, CH 46.6%, C nH m1.5%,

Synthetic gas calorific value: 14.8MJ/m 3

Claims (10)

1. a flammable solid waste chemical chain gasification prepares the method for synthetic gas, it is characterized in that this method implements in a serial fluidized-bed reactor, and said interconnected fluidized bed reactor comprises the fuel reaction device and the air reactor of inner UNICOM; The fuel reaction device is a bubbling fluidized bed; Air reactor is a fluidized-bed riser tube, and this method may further comprise the steps:
1) with flammable solid waste raw material pulverize, subsequent use after the dry pre-treatment;
2) the flammable solid waste generates synthetic gas with oxygen carrier generating gasification reaction in the fuel reaction device, and the required oxygen element of flammable solid waste gasification is from the lattice oxygen in the oxygen carrier molecule;
3) lose oxygen carrier after the lattice oxygen, be transferred to air reactor, in air reactor, oxygen carrier is replied lattice oxygen by high temperature air oxidation again;
4) oxygen carrier after the answer lattice oxygen is taken out of air reactor by high-speed air, returns the fuel reaction device again and recycles, and reacts with flammable solid waste generating gasification once more.
2. flammable solid waste chemical chain gasification as claimed in claim 1 prepares the method for synthetic gas, it is characterized in that: the high-temperature zone of said bubbling fluidized bed links to each other with feeding screw, and air distribution plate is arranged at the bottom of bubbling fluidized bed; The middle part of bubbling fluidized bed is an expanding section, and expanding section is bigger than conversion zone bore, and the flammable solid waste gasifies with the oxygen carrier reaction in bubbling fluidized bed; A revert pipe UNICOM is arranged between bubbling fluidized bed and fluidized-bed riser tube; Wind-distributing pipe is arranged at fluidized-bed riser tube bottom; Material reacts in high temperature air; And taken out of the fluidized-bed riser tube through the fluidized-bed riser tube by high-speed air, the material of taking out of returns bubbling fluidized bed after isolating chip and residue through cyclonic separator; The top of bubbling fluidized bed has a venting hole, and product gas flows out bubbling fluidized bed after cyclonic separator leads to gas-cleaning installation after isolating solid residue from venting hole.
3. according to claim 1 or claim 2 flammable solid waste chemical chain gasification prepares the method for synthetic gas; It is characterized in that: oxygen carrier is formed by transition metal oxide, inert support and adhesive preparation; The oxygen carrier particle for preparing is seated in advance serves as bed material in the bubbling fluidized bed, add hot bed materials.
4. flammable solid waste chemical chain gasification as claimed in claim 3 prepares the method for synthetic gas, it is characterized in that: the transition metal oxide of said preparation oxygen carrier is selected from one of following: NiO, CuO, Fe 2O 3, Mn 3O 4It is one of following that the inert support of said preparation oxygen carrier is selected from: Al 2O 3, SiO 2, MgO, NiAl 2O 4, MgAl 2O 4, ZrO 2The sticker of said preparation oxygen carrier is YSZ.
5. flammable solid waste chemical chain gasification as claimed in claim 2 prepares the method for synthetic gas, it is characterized in that comprising the steps:
1) adopt steam as fluidizing gas; Feed from bubbling fluidized bed bottom, make the carrier of oxygen realize fluidization, after temperature, a fluidisation of treating the bed material all stablized; Flammable solid discarded object raw material adds in the bed material in the bubbling fluidized bed by feeding screw; Flammable solid discarded object raw material is heated, and dewater rapidly in the back, pyrolysis, gasification reaction, and gaseous product, tar and fixed carbon continuation and the carrier of oxygen react, and solid waste is further gasified; Gasification product is derived by the bubbling fluidized bed top, further utilizes through purifying the back;
2) reacted oxygen carrier returns the fluidized-bed riser tube through the revert pipe that is installed in the bubbling fluidized bed middle part; In the fluidized-bed riser tube; The oxygen carrier that is in reduced state is oxidized to the state of oxidation again by the dioxygen oxidation in the high temperature air, replys its lattice oxygen;
3) product gas flows out bubbling fluidized bed after cyclonic separator leads to gas-cleaning installation after isolating solid residue from venting hole; Again the oxygen carrier particle after the oxidation is taken out of the fluidized-bed riser tube by high-speed air, after cyclonic separator is isolated the oxygen carrier chip of gasification reaction residue and breakage, returns in the fuel reaction device, and continuation and flammable solid waste react.
6. flammable solid waste chemical chain gasification as claimed in claim 1 prepares the method for synthetic gas, it is characterized in that: in the said step (2) with bed material heating and be stabilized in the 500-900 ℃ of scope.
7. flammable solid waste chemical chain gasification as claimed in claim 1 prepares the method for synthetic gas, it is characterized in that: in the said step (3) temperature of reaction in the air reactor is controlled in the 600-950 ℃ of scope.
8. interconnected fluidized bed reactor is characterized in that comprising the fluidized-bed reactor of two inner UNICOMs, i.e. fuel reaction device and air reactor; The fuel reaction device is a bubbling fluidized bed, and feeding screw links to each other with the high-temperature zone of bubbling fluidized bed, and air distribution plate is arranged at the bottom of bubbling fluidized bed; The middle part of bubbling fluidized bed is an expanding section, and expanding section is bigger than conversion zone bore; Air reactor is a fluidized-bed riser tube; A revert pipe UNICOM is arranged between bubbling fluidized bed and fluidized-bed riser tube; Wind-distributing pipe is arranged at fluidized-bed riser tube bottom; Material reacts in high temperature air; And taken out of the fluidized-bed riser tube through the fluidized-bed riser tube by high-speed air, the material of taking out of returns bubbling fluidized bed after isolating chip and residue through cyclonic separator; The top of bubbling fluidized bed has a venting hole, and product gas flows out bubbling fluidized bed after cyclonic separator leads to gas-cleaning installation after isolating solid residue from venting hole.
9. interconnected fluidized bed reactor as claimed in claim 8 is characterized in that: the conversion zone at fuel reaction device and air reactor is equipped with external electrical heaters respectively.
10. interconnected fluidized bed reactor as claimed in claim 8 is characterized in that: at the revert pipe middle part sealing chamber is set.
CN 200910042076 2009-08-24 2009-08-24 Method for producing synthesis gas by combustible solid waste chemical chain gasification and interconnected fluidized bed reactor CN101638590B (en)

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