CN112831350A - Device and method for preparing hydrogen-rich synthesis gas from household garbage - Google Patents
Device and method for preparing hydrogen-rich synthesis gas from household garbage Download PDFInfo
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- CN112831350A CN112831350A CN202110022134.3A CN202110022134A CN112831350A CN 112831350 A CN112831350 A CN 112831350A CN 202110022134 A CN202110022134 A CN 202110022134A CN 112831350 A CN112831350 A CN 112831350A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
Abstract
The device comprises a gasification melting part, a synthesis gas purification part and an absorbent regeneration part, can convert the domestic garbage into the hydrogen-rich synthesis gas and realize carbon separation under the condition of not generating secondary pollution, and is a garbage resource utilization technology with high harmless degree and environmental friendliness.
Description
Technical Field
The invention belongs to resource utilization of solid waste and CO2The technical field of separation and trapping, in particular to a method for preparing hydrogen-rich synthesis gas from household garbage and simultaneously realizing CO2A separation apparatus and method.
Background
With the rapid development of economic society and the accelerated layout of urbanization process, domestic garbage produced in various regions worldwide is increased year by year, and if the domestic garbage is not properly disposed, the environment is polluted, and meanwhile, the great waste of energy resources is caused. In 2018, the clearing and transporting amount of domestic garbage in China reaches 2.28 hundred million tons, and the rate of the clearing and transporting amount of domestic garbage is increased by nearly 6-8% every year.
About 52 percent of domestic garbage in the garbage subjected to harmless treatment in China is subjected to sanitary landfill, 45 percent of domestic garbage is subjected to incineration treatment, and the rest harmless treatment amount accounts for about 3 percent. The garbage incineration is a mature garbage heat treatment technology at home and abroad, has the advantages of reduction, high recycling degree, small occupied area and the like, and the harmless treatment occupation of China is improved year by year. However, it is not negligible that the emission of dioxin and heavy metals is easily caused in the process of waste incineration, and although the emission can be inhibited to some extent by means of operation optimization, emission control and the like, the potential hazard of the emission is still controversial, and the fly ash generated by waste incineration is mainly listed in the name of hazardous waste. How to avoid the secondary pollution of the garbage in the harmless treatment process becomes a hotspot of the garbage treatment industry at the present stage.
The gasification and melting technology of domestic garbage, which is the most promising new generation of garbage disposal technology, has been widely studied and rapidly developed in developed countries, especially japan and europe. Compared with the traditional incineration technology, the release of pollutants such as dioxin, heavy metals and the like is further reduced, the metal can be recycled by the generated molten ash, the obtained vitreous residues can be directly used in industries such as cement, building materials and the like, the secondary pollution in the heat treatment process can be greatly reduced, and the purposes of reduction, harmlessness and recycling of municipal waste are really realized.
At present, the most practical garbage gasification and melting technology is high-temperature gasification and direct melting technology internationally. The technology uses a blast furnace iron-making process for reference, realizes the processes of drying, pyrolysis/gasification and ash slag melting of garbage from top to bottom in the same furnace body, and represents Nippon and JFE in Japan. High-temperature gasification direct smelting generally adopts 28-38% of oxygen-enriched air to gasify the garbage, and provides heat required by smelting for the furnace to mix and burn auxiliary fuels such as coke and the like in a certain proportion.
Because oxygen-enriched air is adopted for gasification, the generated synthesis gas contains about 50 percent of nitrogen, the heat loss of flue gas is larger, the combustible components are relatively lower, and the application range of the synthesis gas is limited. In addition, corrosive gas is generated in the garbage gasification process, and the high-temperature corrosivity of the acid gas limits the efficiency of garbage resource utilization. Under the promotion of achieving the goal of carbon neutralization, how to reduce carbon emission and achieve carbon separation in the process of treating the household garbage will become the focus of attention. Aiming at the defects of the technologies, the development of a garbage gasification treatment technology with high energy utilization efficiency and small environmental pollution is urgently needed.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a device and a method for preparing hydrogen-rich synthetic gas from household garbage, and the device or the method can be used for simply and efficiently obtaining the hydrogen-rich synthetic gas with higher combustible component content and simultaneously realizing CO2Separation of (4).
Means for solving the problems
Specifically, the present invention solves the technical problems to be solved by the present invention by the following means.
[1] An apparatus for producing a hydrogen-rich syngas from household waste, the apparatus comprising:
a gasification melting section comprising a gasification melting furnace configured to convert the domestic waste into a raw syngas and a molten slag, the gasification melting furnace having a combustible gas and water vapor inlet and an oxygen inlet;
a syngas purification section comprising a purification column and downstream thereof a first gas-solid separator; wherein the purification tower is configured to contact the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; the first gas-solid separator is configured to carry out gas-solid separation on the refined synthesis gas and the inactivated absorbent, and a gas outlet of the first gas-solid separator is connected with the combustible gas and water vapor inlets; and
an absorbent regeneration section comprising a regeneration column and a second gas-solid separator downstream thereof; the regeneration tower is configured to pyrolyze and regenerate the deactivated absorbent to convert the deactivated absorbent into regenerated absorbent and CO-rich absorbent2The gas of (4); the second gas-solid separator is configured to separate the regenerated absorbent and the CO rich gas2The gas is subjected to gas-solid separation, and a solid outlet of the gas-solid separation is connected with a purifying tower feed back port which is arranged on the purifying tower and used for receiving the absorbent.
[2] The apparatus according to [1], wherein the gasification melting furnace comprises a gasification melting reaction zone, and the gasification melting reaction zone comprises a drying zone, a pyrolysis zone, a gasification zone, a combustion zone and a melting zone in sequence from top to bottom.
[3] The apparatus according to [1], wherein the synthesis gas purification section further comprises a gas-liquid separator located downstream of the first gas-solid separator, an inlet of the gas-liquid separator is connected with a flow dividing device arranged between a gas outlet of the first gas-solid separator and the combustible gas and steam inlet, and the gas-liquid separator is configured to separate condensed components from the gas from the first gas-solid separator to obtain the dry hydrogen-rich synthesis gas.
[4] The apparatus according to [1], wherein the purification column is operated in a fluidized mode, preferably in a bubbling bed, a turbulent bed or a fast bed, and the operation temperature is 500-.
[5] The apparatus according to [1], wherein a flow dividing means is further provided at a position downstream of the solids outlet of the first gas-solid separator and upstream of the regeneration section, and is connected to the discharge opening, and configured to discharge at least a portion of the deactivated absorbent through the discharge opening.
[6] The apparatus according to [1], wherein the regeneration column is operated in a fluidized manner, preferably in a bubbling bed, a turbulent bed or a fast bed, and the operation temperature is 850-.
[7] The apparatus according to [1], further comprising a fresh absorbent supply portion comprising a fresh absorbent bin and an absorbent conveyor connected thereto, wherein the absorbent conveyor is connected to a fresh absorbent feed port provided to the regeneration tower.
[8] An apparatus for producing a hydrogen-rich synthesis gas from domestic waste, the apparatus comprising a gasification melting section, a synthesis gas purification section, an absorbent regeneration section and a fresh absorbent supply section, wherein the gasification melting section comprises an updraft gasification melting furnace (1) equipped with a sealable domestic waste feeder (6) and having a raw synthesis gas outlet (10), a liquid slag discharge port (13), an oxygen gas inlet port (12) and a combustible gas and water vapor inlet port (11);
the synthesis gas purification part comprises a purification tower (2), a first cyclone separator (4) and a gas-liquid separator (7); the purification tower (2) is provided with a purification tower outlet (15), a purification tower air inlet (14) connected with the crude synthesis gas outlet (10), and a purification tower feed back opening (21); the inlet of the first cyclone separator (4) is connected with the outlet (15) of the purification tower, the gas outlet (16) of the first cyclone separator is respectively connected with the inlet of the gas-liquid separator (7) and the inlet (11) of the combustible gas and the water vapor through a flow dividing device, and the solid outlet of the first cyclone separator (4) is respectively connected with the discharge opening (19) of the deactivation absorbent and the feed back opening (18) of the regeneration tower through the flow dividing device; the gas-liquid separator (7) is also provided with a gas-liquid separator outlet (17) for discharging the dry hydrogen-rich synthesis gas;
the absorbent regeneration part comprises a regeneration tower (3) and a second cyclone separator (5); the regeneration tower (3) is provided with a regeneration tower fluidized medium air inlet (23), a regeneration tower feed back port (18) connected with a solid outlet of the first cyclone separator (4), a regeneration tower outlet (20) connected with an inlet of the second cyclone separator (5), the solid outlet of the second cyclone separator (5) is connected with a purification tower feed back port (21), and a second cyclone separator gas outlet (22) is further arranged on the second cyclone separator (5) and used for enriching CO2The gas of (2) is discharged;
the fresh absorbent supply part comprises a fresh absorbent bin (8) and an absorbent conveyer (9), and the fresh absorbent bin (8) is connected with a fresh absorbent feeding hole (24) of the regeneration tower, which is arranged on the regeneration tower (3), through the absorbent conveyer (9).
[9] A process for producing a hydrogen-rich synthesis gas comprising the steps of:
a gasification melting step: gasifying and melting the household garbage in the presence of combustible gas, steam and oxygen to convert the household garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: contacting the raw synthesis gas with an absorbent with a transition metal loaded on the surface to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; gas-solid separation is carried out on the material containing the refined synthesis gas and the inactivated absorbent; conveying at least a portion of the refined syngas to a gasification melting step; optionally separating condensed components from another portion of the refined synthesis gas to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: carrying out pyrolysis regeneration on the inactivated absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials; and conveying the regenerated absorbent to a synthesis gas purification step for recycling.
[10] A process for producing a hydrogen-rich synthesis gas by using the apparatus as defined in any one of [1] to [8], comprising the steps of:
a gasification melting step: supplying the domestic garbage, combustible gas and water vapor and oxygen to a gasification melting part, gasifying and melting the domestic garbage in the gasification melting part, and converting the domestic garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: supplying the raw synthesis gas from the gasification and melting part to a synthesis gas purification part, and contacting the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO2And combining at least a portion of the acid gas with an absorbent to produce a refined synthesis gas and a deactivated absorbent; carrying out gas-solid separation on the material containing the refined synthesis gas and the inactivated absorbent;
conveying at least a portion of the refined syngas to a gasification melting section;
optionally feeding another part of the refined synthesis gas to a gas-liquid separator for separation of condensed components to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: from the syngas clean-up sectionThe deactivated absorbent is supplied to the absorbent regeneration section to perform pyrolysis regeneration of the absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials;
and conveying the regenerated absorbent to a synthesis gas purification part for recycling.
[11] The method according to [9] or [10], wherein in the gasification and melting step, the household garbage is dried, pyrolyzed, gasified, combusted and melted from top to bottom, and the melting temperature is 1300-1800 ℃.
[12] The process according to [9] or [10], wherein at least a part of the combustible gas and steam in the gasification melting step is derived from the refined synthesis gas produced in the synthesis gas purification step, and the heat generated by the complete combustion of the combustible gas from the refined synthesis gas is 20-50% of the heat generated by the complete combustion of the domestic garbage.
[13] The process according to [9] or [10], wherein the mass ratio of the steam to the domestic waste in the gasification melting step is 0.5 to 3.0.
[14] The process according to [9] or [10], wherein the ratio of the amount of oxygen in the gasification melting step to the chemical oxygen demand of the domestic waste is 0.1 to 0.4.
[15] The method according to [9] or [10], wherein the transition metal-surface-supported absorbent is a transition metal-surface-supported calcium carbonate ore.
[16] The process according to [15], wherein the calcium carbonate ore is one or more selected from limestone, calcite and aragonite, the transition metal is nickel, copper, cobalt and/or iron, and the loading of the transition metal is 1-10% of the calcium carbonate ore.
[17] The process according to [9] or [10], wherein the contacting of the raw synthesis gas with the absorbent is carried out at a temperature of 500-700 ℃.
[18] The process according to [9] or [10], wherein the pyrolysis of the absorbent is carried out at a temperature of 850-1000 ℃.
[19] The method according to [9] or [10], further comprising supplying fresh absorbent to the absorbent regeneration step.
[20] The method according to [9] or [10], further comprising a step of crushing the domestic waste before the gasification melting step.
[21]According to [9]]Or [10]]The method of, wherein the dry hydrogen-rich syngas comprises H2CO and methane, wherein H2The volume content of (A) is 70-90%, the volume content of CO is 5-20%, and the volume content of methane is 5-10%.
ADVANTAGEOUS EFFECTS OF INVENTION
Compared with the prior art, the invention has the following advantages and beneficial effects: the device integrates gasification and melting of the household garbage, purification of the synthesis gas and regeneration of the absorbent, so that the device can be used for producing high-quality hydrogen-rich synthesis gas from the household garbage more simply and efficiently, improving the resource utilization efficiency of the household garbage, reducing the tar content in the synthesis gas, reducing the high-temperature corrosivity of the flue gas and realizing CO (carbon monoxide) simultaneously2Trapping and separation.
Specifically, the method adopts water vapor as a gasification medium, which is beneficial to obtaining the synthesis gas with higher hydrogen content; oxygen and the hydrogen-rich synthesis gas prepared by the method are introduced to the bottom of the gasification melting furnace to be combusted so as to provide heat required by gasification melting and gasified water vapor, so that the input amount of an external heat source is obviously reduced; calcium carbonate ore with transition metal loaded on the surface is adopted, and CaO/CaCO is utilized3Cyclic realization of para-CO2The acid gas such as H in the synthesis gas of CaO2S and HCl also have good adsorption effect, and can purify the synthesis gas and reduce the high-temperature corrosivity of the synthesis gas; in addition, the loaded transition metal can carry out catalytic reforming on tar generated by gasification, so that the tar content is obviously reduced, and the combustible component content and the heat value of the synthesis gas are improved.
Drawings
FIG. 1 is a schematic view of the apparatus and process for preparing hydrogen-rich syngas from domestic garbage according to the present invention.
Description of the reference numerals
In the figure: 1-updraft gasification melting furnace; 2-a purification tower; 3-a regeneration tower; 4-cyclone separator No. one; 5-second cyclone separator; 6-a domestic waste feeder; 7-gas-liquid separator; 8-fresh absorbent silo; 9-absorbent conveyor; 10-outlet of the raw synthesis gas; 11-combustible gas and water vapour inlet; 12-oxygen inlet; 13-liquid slag discharge port; 14-a purge column gas inlet; 15-outlet of the purification tower; 16-cyclone gas outlet; 17-gas liquid separator outlet; 18-a regeneration tower feed back port; 19-a deactivated absorbent discharge; 20-the outlet of the regeneration column; 21-a feed back port of the purification tower; 22-second cyclone gas outlet; 23-a regenerator fluidized medium inlet; 24-fresh absorbent feed inlet of regeneration tower.
Detailed Description
< apparatus >
The invention aims to provide a device for preparing hydrogen-rich synthesis gas from household garbage, which comprises the following components:
a gasification melting section comprising a gasification melting furnace configured to convert the domestic waste into a raw syngas and a molten slag, the gasification melting furnace having a combustible gas and water vapor inlet and an oxygen inlet;
a syngas purification section comprising a purification column and downstream thereof a first gas-solid separator; wherein the purification tower is configured to contact the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; the first gas-solid separator is configured to carry out gas-solid separation on the refined synthesis gas and the inactivated absorbent, and a gas outlet of the first gas-solid separator is connected with the combustible gas and water vapor inlets; and
an absorbent regeneration section comprising a regeneration column and a second gas-solid separator downstream thereof; the regeneration tower is configured to pyrolyze and regenerate the deactivated absorbent to convert the deactivated absorbent into regenerated absorbent and CO-rich absorbent2The gas of (4); the second gas-solid separator is configured to separate the regenerated absorbent and the CO rich gas2The gas is subjected to gas-solid separation, and a solid outlet of the gas-solid separation device is arranged in the purification towerThe feed back port of the purification tower for receiving the absorbent is connected.
The various parts of the apparatus of the present invention will be described in detail below.
Gasification of molten parts
The gasification and melting part comprises a gasification and melting furnace for gasifying and melting the household garbage, and is preferably an updraft gasification and melting furnace. The gasification melting furnace comprises: a domestic garbage feeding port, a gasification and melting reaction zone, a combustible gas and water vapor inlet, an oxygen inlet, a gas outlet and a liquid slag discharging port. The household garbage feeding port is arranged at the top, the gas outlet is arranged on the side wall of the top, the liquid slag discharging port is arranged at the bottom, and the combustible gas and water vapor inlet and the oxygen inlet are arranged above the liquid slag discharging port.
The gasification and melting reaction zone sequentially comprises a drying zone, a pyrolysis zone, a gasification zone, a combustion zone and a melting zone from top to bottom. In some embodiments, there is no strict boundary between the reaction zones, and there is an overlapping region between adjacent reaction zones, where multiple reactions are simultaneously performed. For example, in the overlapping area between the drying zone and the pyrolysis zone, the drying and pyrolysis of the domestic waste are carried out simultaneously.
The domestic garbage, high-temperature steam and oxygen are subjected to gasification reaction in a gasification melting furnace, and finally fall into a melting area at the bottom of a hearth and are discharged from a liquid slag discharge port at the bottom after the processes of drying, pyrolysis, gasification, combustion and melting from top to bottom. The temperature of the bottom melting zone of the gasification melting furnace is controlled at 1300-1800 ℃. The discharged slag can be directly used as building materials after being cooled.
Syngas clean-up section
In the apparatus of the present invention, the synthesis gas purification section comprises a purification column, a first gas-solid separator and optionally a gas-liquid separator.
The purification tower comprises: a gas inlet for receiving raw synthesis gas from the gasification melting section, a purge column feed back for receiving absorbent, an absorption zone, and an outlet for discharging material. Wherein the absorption zone contains an absorbent with transition metal loaded on the surface, and the raw synthesis gas is contacted with the absorbent. The purification tower preferably adopts a fluidization operation mode, and the operation temperature is 500-700 ℃. The operation of the purification column is further preferably a bubbling bed, a turbulent bed or a fast bed.
A first gas-solid separator is located downstream of the purification column and has an inlet for receiving the effluent from the purification column, a gas outlet for discharging the refined synthesis gas, and a solids outlet for discharging the deactivated absorbent.
A gas-liquid separator is located downstream of the first gas-solid separator and has an inlet for receiving the refined syngas and an outlet for discharging the dry hydrogen-rich syngas.
A flow splitting device is also optionally provided between the gas outlet of the first gas-solid separator, the inlet of the gas-liquid separator and the combustible gas and steam inlet, configured to deliver at least a portion of the refined syngas to the gasification melting section and optionally another portion to the gas-liquid separator.
A flow dividing device is also provided downstream of the solids outlet of the first gas-solid separator and upstream of the regeneration section, said flow dividing device being connected to the discharge opening and configured to discharge at least a portion of the deactivated sorbent through the discharge opening out of the apparatus of the invention.
Absorbent regeneration section
The absorbent regeneration part comprises a regeneration tower and a second gas-solid separator. The regeneration tower has: a solids inlet to receive deactivated sorbent from the syngas cleanup section, a fluidizing medium inlet, a pyrolysis zone, and an outlet to discharge material. The pyrolysis regeneration of the deactivated absorbent is carried out in a regeneration column, which is preferably operated in a fluidized manner at an operating temperature of 850-. The regeneration column is further preferably operated in a bubbling bed, a turbulent bed or a fast bed.
The second gas-solid separator is located downstream of the regeneration tower and has an inlet for receiving the regeneration tower discharge, a gas outlet and a solids outlet, wherein the solids outlet is connected to the purification tower feed back of the purification section which receives the absorbent.
The deactivated absorbent from the purification part is pyrolyzed and regenerated in a regeneration tower, and the discharged material from the regeneration tower is subjected to gas-solid separation by a second gas-solid separator positioned at the downstream of the regeneration towerThe regenerated absorbent obtained by separation is conveyed to a purification part through a solid outlet for recycling, and CO rich in separated CO is obtained2Is discharged from the apparatus of the invention via a gas outlet and optionally subjected to further fixing treatment.
In the apparatus of the present invention, the first and second gas-solid separators may be any apparatus known in the art capable of gas-solid separation, such as cyclone separator, gravity settler, inertial separator, and various electric dust-removing apparatuses, and may be formed by connecting a plurality of these apparatuses in parallel or in series.
The gas-liquid separator of the present invention may be any device known in the art capable of achieving gas-liquid separation, such as a condenser, a centrifugal separator, and the like.
In one embodiment, the apparatus of the present invention may further comprise a fresh absorbent supply section comprising a fresh absorbent silo and an absorbent conveyor connected thereto. In this embodiment, the regeneration tower is further provided with a fresh absorbent feeding port connected to the absorbent conveyor to supply fresh absorbent to the absorbent regeneration section.
In one embodiment, the apparatus of the present invention may further comprise a crushing section for the domestic waste, which is crushed before being supplied to the gasification melting section. Crushing may be performed using various equipment known in the art, such as universal crushers, shear crushers, refuse shredders, and the like.
The device can convert the household garbage into the hydrogen-rich synthesis gas without generating secondary pollution and simultaneously realize carbon separation, and is a garbage resource utilization technology with high harmless degree and environmental friendliness.
Preferred embodiments of the apparatus of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the apparatus of the present invention includes a gasification melting section, a syngas cleaning section, an absorbent regeneration section, and a fresh absorbent supply section. The gasification melting part comprises an updraft type gasification melting furnace 1, the top of the updraft type gasification melting furnace is provided with a sealable domestic garbage feeder 6, the side wall of the top of the updraft type gasification melting furnace is provided with a crude synthesis gas outlet 10, the bottom of the updraft type gasification melting furnace is provided with a liquid slag discharge port 13, and an oxygen inlet 12 and a combustible gas and water vapor inlet 11 are arranged above the liquid slag discharge port 13.
The synthesis gas purification part comprises a purification tower 2, a first cyclone separator 4 and a gas-liquid separator 7. The top of the purification tower 2 is provided with a purification tower outlet 15, the bottom is provided with a purification tower air inlet 14 connected with the crude synthesis gas outlet 10, and the side wall of the bottom is also provided with a purification tower feed back port 21. The inlet of the first cyclone separator 4 is connected with the outlet 15 of the purification tower, the gas outlet 16 of the first cyclone separator is respectively connected with the inlet of the gas-liquid separator 7 and the combustible gas and water vapor inlet 11 through a flow dividing device, and the solid outlet of the first cyclone separator 4 is respectively connected with the discharge opening 19 of the inactivation absorbent and the feed back 18 of the regeneration tower through a flow dividing device. The gas-liquid separator 7 is also provided with a gas-liquid separator outlet 17 for discharging the hydrogen-rich synthesis gas.
The absorbent regeneration part comprises a regeneration tower 3 and a second cyclone separator 5. The bottom of the regeneration tower 3 is provided with a regeneration tower fluidized medium inlet 23, the side wall of the bottom is provided with a regeneration tower feed back port 18 connected with the solid outlet of the first cyclone separator 4, and the upper part is provided with a regeneration tower outlet 20 connected with the inlet of the second cyclone separator 5. The solid outlet of the second cyclone separator 5 is connected with the feed back 21 of the purification tower, and the second cyclone separator 5 is also provided with a second cyclone separator gas outlet 22 for separating CO2And (4) discharging.
The fresh absorbent supply part comprises a fresh absorbent bin 8 and an absorbent conveyer 9, and the fresh absorbent bin 8 is connected with a regeneration tower fresh absorbent feed port 24 arranged on the bottom side wall of the regeneration tower 3 through the absorbent conveyer 9.
< method >
It is another object of the present invention to provide a process for the preparation of a hydrogen rich synthesis gas comprising the steps of:
a gasification melting step: gasifying and melting the household garbage in the presence of combustible gas, steam and oxygen to convert the household garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: the raw synthesis gas is loaded withContacting transition metal absorbent to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; gas-solid separation is carried out on the material containing the refined synthesis gas and the inactivated absorbent; conveying at least a portion of the refined syngas to a gasification melting step; optionally separating condensed components from another portion of the refined synthesis gas to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: carrying out pyrolysis regeneration on the inactivated absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials; and conveying the regenerated absorbent to a synthesis gas purification step for recycling.
Specifically, the invention provides a method for preparing hydrogen-rich synthesis gas by using the device, which comprises the following steps:
a gasification melting step: supplying the domestic garbage, combustible gas and water vapor and oxygen to a gasification melting part, gasifying and melting the domestic garbage in the gasification melting part, and converting the domestic garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: supplying the raw synthesis gas from the gasification and melting part to a synthesis gas purification part, and contacting the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO2And combining at least a portion of the acid gas with an absorbent to produce a refined synthesis gas and a deactivated absorbent; carrying out gas-solid separation on the material containing the refined synthesis gas and the inactivated absorbent;
conveying at least a portion of the refined syngas to a gasification melting section;
optionally conveying another part of the refined synthesis gas to a gas-liquid separator for water vapor separation to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: feeding the deactivated absorbent from the syngas clean-up section to an absorbent regeneration section for pyrolytic regeneration of absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials;
and conveying the regenerated absorbent to a synthesis gas purification part for recycling.
The individual steps of the process of the invention will be described in detail below.
According to the method, the household garbage is subjected to gasification reaction with high-temperature steam and oxygen in a gasification melting furnace of a gasification melting part, and finally falls into a melting area at the bottom of a hearth and is discharged from a liquid slag discharge port at the bottom after the processes of drying, pyrolysis, gasification, combustion and melting are carried out from top to bottom. The temperature of the bottom melting zone of the gasification melting furnace is controlled at 1300-1800 ℃; when the temperature is lower than 1300 ℃, part of high-melting-point ash slag is difficult to form a molten state, so that the slag discharge is difficult, and when the temperature is higher than 1800 ℃, the required input energy is too high, so that the economic operation of the system is influenced.
Combustible gas and gasification steam are fed from a combustible gas and steam inlet at the bottom of the gasification melting furnace, wherein at least one part of the combustible gas and the gasification steam is from the refined synthesis gas obtained by the synthesis gas purification part, and the heat generated by the complete combustion of the combustible gas from the refined synthesis gas is 20-50% of the heat generated by the complete combustion of the domestic garbage. The proportion of the combustible gas from the refined synthesis gas in the combustible gas can be properly adjusted according to different operation modes, for example, when the system is expected to operate to obtain higher yield of the hydrogen-rich synthesis gas, the proportion of the combustible gas from the refined synthesis gas in the combustible gas should be selected to be a lower value, and when the system is expected to realize self-heating operation and the garbage harmless treatment process is emphasized rather than the yield of the hydrogen-rich synthesis gas, the proportion of the combustible gas from the refined synthesis gas in the combustible gas should be selected to be a higher value, and even the refined synthesis gas is completely sent to the gasification melting furnace to be combusted so as to avoid higher demand of an external heat source.
The steam as gasification medium has a great influence on the hydrogen content in the synthesis gas, and there is an optimum steam addition for different domestic waste compositions and gasification temperatures, preferably the mass ratio of steam to domestic waste is 0.5-3.0, preferably 0.8-1.5.
Oxygen is fed from an oxygen inlet at the bottom of the gasification melting furnace, and the ratio of the chemical oxygen demand of the added oxygen to the chemical oxygen demand of the domestic garbage is 0.1-0.4, preferably 0.2-0.3. The main purposes of adding oxygen are two, namely, the combustible gas added at the bottom is promoted to combust to provide heat for a melting zone, the incomplete gasification products of the household garbage at the bottom of a hearth, such as coke and the like, are promoted to combust to realize complete treatment and provide partial heat, and meanwhile, the residual oxygen can participate in the gasification reaction of the household garbage at the upper part of the gasification melting furnace. The introduction amount of oxygen also has a relatively good range, the combustion of bottom combustible components cannot be realized when the introduction amount is too low, and the heat required by the hearth can be maintained, and the proportion of the combustible components in the crude synthesis gas is reduced when the introduction amount is too high, so that the gasification efficiency is lowered.
The raw synthesis gas produced by gasifying the domestic waste is discharged from the gasification and melting section and then sent to the synthesis gas purification section. In a synthesis gas purification section, the raw synthesis gas is contacted with an absorbent having a transition metal supported on the surface thereof while CO is carried out2The separation of the acid gases, the removal of the acid gases and the catalytic reforming of the gasified tar to obtain the refined synthesis gas, wherein the acid gases are mainly HCl and H2S and the like. CO 22The separation and absorption and the removal of the acid gas are mainly completed by an active component CaO of an alkaline absorbent, and the alkaline absorbent also has a certain catalytic cracking effect on tar generated by gasification, but has a limited effect. The effective catalytic cracking and reforming of tar is mainly completed by transition metal loaded on the surface of absorbent.
The contacting of the raw synthesis gas with the absorbent is carried out in a purification column, which preferably operates in a fluidized mode, further preferred modes of operation include bubbling beds, turbulent beds, fast beds, etc. The contact of the crude synthesis gas and the absorbent is carried out at the temperature of 500-700 ℃, and when the temperature is too high, CaO absorbs CO2And the efficiency of acid gas is reduced, so that the circulation amount of the required absorbent is increased, the catalytic cracking and reforming efficiency of tar is reduced when the temperature is too low, the quality of the synthesis gas is influenced, and in addition, the comprehensive utilization of system energy is not facilitated when the temperature is too low.
And the material containing the refined synthesis gas and the inactivated absorbent discharged from the purification tower is subjected to gas-solid separation by the first gas-solid separator. All or part of the separated refined synthesis gas enters a gasification melting part through a combustible gas and steam inlet to participate in combustion and gasification, and the other part of the refined synthesis gas (if existing) is separated by a gas-liquid separator to obtain a dry hydrogen-rich synthesis gas after a condensed component.
And (3) conveying part or all of the deactivated absorbent subjected to gas-solid separation to an absorbent regeneration part for pyrolysis regeneration of the absorbent. The pyrolysis of the absorbent is carried out in a regeneration tower which adopts a fluidization operation mode, and further preferable operation modes comprise a bubbling bed, a turbulent bed, a fast bed and the like. Pyrolysis of the absorbent is carried out at the temperature of 850-1000 ℃, when the temperature is too low, the deactivated absorbent cannot be effectively regenerated, and when the temperature is too high, external heat input during system operation is increased, and energy consumption is increased. The deactivated absorbent may be discharged at a process point between the syngas clean-up section and the absorbent regeneration section after prolonged use.
The discharge of the regeneration tower contains regenerated absorbent and CO2The material is subjected to gas-solid separation through a second gas-solid separator, the separated regenerated absorbent is conveyed to a synthesis gas purification part for cyclic utilization, and the separated CO-rich gas is rich in CO2Is discharged from an outlet at the top of the second gas-solid separator.
In one embodiment, the process of the present invention further comprises the step of feeding fresh absorbent to the absorbent regeneration section. Specifically, the fresh absorbent stored in the fresh absorbent silo is transported from the inlet port to the absorbent regeneration section via an absorbent conveyor, preferably a pellet conveyor.
In the method of the present invention, the household garbage as the raw material generally includes various garbage generated by daily life, including but not limited to kitchen garbage, paper, plastics, fabrics, biomass, and the like. Generally, all organic matter in the domestic waste can be used as raw material for producing hydrogen-rich synthesis gas.
The method of the present invention may further comprise a step of crushing the domestic waste, which is crushed before being supplied to the gasification melting section. Crushing can be carried out using various methods known in the art, such as by universal crushers, shear crushers, refuse shredders, and the like.
The absorbent used in the present invention is preferably in the form of particles, and more preferably calcium carbonate ore having a transition metal supported on the surface thereof. The calcium carbonate ore is one or more selected from limestone, calcite and aragonite. Raw ore is preferred because of its low cost and ready availability. The transition metal loaded on the surface of the absorbent is nickel, copper, cobalt and/or iron, and the mass ratio of the transition metal to the calcium carbonate ore is 1-10%. The transition metal load has an optimal range, the high-efficiency catalytic action on tar cannot be formed due to the low load, and the high load causes the high consumption of the transition metal and increases the use cost of the absorbent.
The dry hydrogen-rich synthesis gas obtained by the present invention consists mainly of H2CO and methane, wherein H2The volume content of (A) is 70-90%, the volume content of CO is 5-20%, and the volume content of methane is 5-10%.
Preferred embodiments of the method of the present invention are further described below with reference to the accompanying drawings.
Referring to fig. 1, domestic garbage, combustible gas and water vapor, and oxygen are supplied to the updraft gasification-melting furnace 1 via a domestic garbage feeder 6, a combustible gas and water vapor inlet 11, and an oxygen inlet 12, respectively. In the updraft gasification melting furnace 1, the domestic garbage, high-temperature steam and oxygen are subjected to gasification reaction, and the domestic garbage finally falls into a high-temperature melting area at the bottom of a hearth and is discharged from a liquid slag discharge port 13 at the bottom through drying, pyrolysis, gasification, combustion and melting processes from top to bottom.
The raw synthesis gas generated by the gasification of the domestic garbage is discharged from a raw synthesis gas outlet 10, and then is conveyed into the purification tower 2 through a purification tower air inlet 14 to contact with an absorbent with transition metal loaded on the surface for CO2The separation of the acid gas and the catalytic reforming of the gasified tar are converted into the refined synthesis gas, and simultaneously, the absorbent and the CO are mixed2And the acid gas reacts to be converted into the inactive absorbent. The material containing the refined synthesis gas and the inactivated absorbent in the purification tower is discharged from an outlet 15 of the purification tower and enters a first cyclone separator 4 for gas-solid separation. The fine synthesis gas obtained after separation is discharged from a gas outlet 16 of the first cyclone separatorOne part is conveyed to the gas-liquid separator 7 for gas-liquid separation and then discharged through the gas-liquid separator outlet 17, and the other part is conveyed to the updraft type gasification melting furnace 1 through the combustible gas and steam inlet 11.
The deactivated absorbent obtained after separation is conveyed to the regeneration tower 3 through a regeneration tower feed back port 18 for pyrolysis, and the CO-containing absorbent obtained after pyrolysis2And the regenerated absorbent material is discharged from the regeneration tower outlet 20 and then conveyed to the second cyclone separator 5 for gas-solid separation, the separated regenerated absorbent returns to the purification tower 2 through the purification tower feed back port 21 for recycling, and the separated gas is discharged as high-concentration flue gas through the second cyclone separator gas outlet 22.
Industrial applicability
The invention has wide application prospect in the field of domestic garbage treatment.
Claims (21)
1. An apparatus for producing a hydrogen-rich syngas from household waste, the apparatus comprising:
a gasification melting section comprising a gasification melting furnace configured to convert the domestic waste into a raw syngas and a molten slag, the gasification melting furnace having a combustible gas and water vapor inlet and an oxygen inlet;
a syngas purification section comprising a purification column and downstream thereof a first gas-solid separator; wherein the purification tower is configured to contact the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; the first gas-solid separator is configured to carry out gas-solid separation on the refined synthesis gas and the inactivated absorbent, and a gas outlet of the first gas-solid separator is connected with the combustible gas and water vapor inlets; and
an absorbent regeneration section comprising a regeneration column and a second gas-solid separator downstream thereof; the regeneration tower is configured to pyrolyze and regenerate the deactivated absorbent to convert the deactivated absorbent into regenerated absorbent and CO-rich absorbent2The gas of (4);the second gas-solid separator is configured to separate the regenerated absorbent and the CO rich gas2The gas is subjected to gas-solid separation, and a solid outlet of the gas-solid separation is connected with a purifying tower feed back port which is arranged on the purifying tower and used for receiving the absorbent.
2. The apparatus of claim 1, wherein the gasification melter comprises a gasification melting reaction zone comprising, in order from top to bottom, a drying zone, a pyrolysis zone, a gasification zone, a combustion zone, and a melting zone.
3. The apparatus of claim 1 wherein the syngas cleanup section further comprises a gas-liquid separator downstream of the first gas-solid separator, an inlet of the gas-liquid separator being connected to a flow splitting device disposed between the gas outlet of the first gas-solid separator and the combustible gas and steam inlet, and configured to effect separation of condensed components from the gas from the first gas-solid separator to yield a dry hydrogen-enriched syngas.
4. The apparatus according to claim 1, wherein the purification column is operated in a fluidized mode, preferably in a bubbling bed, a turbulent bed or a fast bed, and the operation temperature is 500-.
5. The apparatus according to claim 1, wherein a flow dividing device is further provided downstream of the solids outlet of the first gas-solid separator and upstream of the regeneration section, and is connected to the discharge opening and configured to discharge at least a portion of the deactivated sorbent through the discharge opening.
6. The apparatus according to claim 1, wherein the regeneration column is operated in a fluidized manner, preferably in a bubbling bed, a turbulent bed or a fast bed, at an operating temperature of 850-.
7. The apparatus according to claim 1, further comprising a fresh absorbent supply portion comprising a fresh absorbent bin and an absorbent conveyor connected thereto, wherein the absorbent conveyor is connected to a fresh absorbent feed port provided in the regeneration column.
8. An apparatus for producing a hydrogen-rich synthesis gas from domestic waste, the apparatus comprising a gasification melting section, a synthesis gas purification section, an absorbent regeneration section and a fresh absorbent supply section, wherein the gasification melting section comprises an updraft gasification melting furnace (1) equipped with a sealable domestic waste feeder (6) and having a raw synthesis gas outlet (10), a liquid slag discharge port (13), an oxygen gas inlet port (12) and a combustible gas and water vapor inlet port (11);
the synthesis gas purification part comprises a purification tower (2), a first cyclone separator (4) and a gas-liquid separator (7); the purification tower (2) is provided with a purification tower outlet (15), a purification tower air inlet (14) connected with the crude synthesis gas outlet (10), and a purification tower feed back opening (21); the inlet of the first cyclone separator (4) is connected with the outlet (15) of the purification tower, the gas outlet (16) of the first cyclone separator is respectively connected with the inlet of the gas-liquid separator (7) and the inlet (11) of the combustible gas and the water vapor through a flow dividing device, and the solid outlet of the first cyclone separator (4) is respectively connected with the discharge opening (19) of the deactivation absorbent and the feed back opening (18) of the regeneration tower through the flow dividing device; the gas-liquid separator (7) is also provided with a gas-liquid separator outlet (17) for discharging the dry hydrogen-rich synthesis gas;
the absorbent regeneration part comprises a regeneration tower (3) and a second cyclone separator (5); the regeneration tower (3) is provided with a regeneration tower fluidized medium air inlet (23), a regeneration tower feed back port (18) connected with a solid outlet of the first cyclone separator (4), a regeneration tower outlet (20) connected with an inlet of the second cyclone separator (5), the solid outlet of the second cyclone separator (5) is connected with a purification tower feed back port (21), and a second cyclone separator gas outlet (22) is further arranged on the second cyclone separator (5) and used for enriching CO2The gas of (2) is discharged;
the fresh absorbent supply part comprises a fresh absorbent bin (8) and an absorbent conveyer (9), and the fresh absorbent bin (8) is connected with a fresh absorbent feeding hole (24) of the regeneration tower, which is arranged on the regeneration tower (3), through the absorbent conveyer (9).
9. A process for producing a hydrogen-rich synthesis gas comprising the steps of:
a gasification melting step: gasifying and melting the household garbage in the presence of combustible gas, steam and oxygen to convert the household garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: contacting the raw synthesis gas with an absorbent with a transition metal loaded on the surface to make CO in the raw synthesis gas2And at least a portion of the acid gas is combined with an absorbent and the gasified tar is catalytically reformed to obtain a refined syngas and an inactivated absorbent; gas-solid separation is carried out on the material containing the refined synthesis gas and the inactivated absorbent; conveying at least a portion of the refined syngas to a gasification melting step; optionally separating condensed components from another portion of the refined synthesis gas to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: carrying out pyrolysis regeneration on the inactivated absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials; and conveying the regenerated absorbent to a synthesis gas purification step for recycling.
10. A method for producing a hydrogen-rich synthesis gas using the apparatus of any one of claims 1 to 8, comprising the steps of:
a gasification melting step: supplying the domestic garbage, combustible gas and water vapor and oxygen to a gasification melting part, gasifying and melting the domestic garbage in the gasification melting part, and converting the domestic garbage into crude synthesis gas and molten slag;
and (3) synthetic gas purification: supplying the raw synthesis gas from the gasification and melting part to a synthesis gas purification part, and contacting the raw synthesis gas with an absorbent having a transition metal supported on the surface thereof to make CO2And combining at least a portion of the acid gas with an absorbent to produce a refined synthesis gas and a deactivated absorbent; carrying out gas-solid separation on the material containing the refined synthesis gas and the inactivated absorbent;
conveying at least a portion of the refined syngas to a gasification melting section;
optionally feeding another part of the refined synthesis gas to a gas-liquid separator for separation of condensed components to obtain a dry hydrogen-rich synthesis gas;
an absorbent regeneration step: feeding the deactivated absorbent from the syngas clean-up section to an absorbent regeneration section for pyrolytic regeneration of absorbent; for the pyrolysis obtained absorbent and CO2Carrying out gas-solid separation on the materials;
and conveying the regenerated absorbent to a synthesis gas purification part for recycling.
11. The method as claimed in claim 9 or 10, wherein in the gasification and melting step, the domestic garbage goes through drying, pyrolysis, gasification, combustion and melting processes from top to bottom, and the melting temperature is 1300-1800 ℃.
12. The process according to claim 9 or 10, wherein at least a portion of the combustible gas and steam in the gasification melting step is derived from the refined syngas produced in the syngas purification step, and the heat produced by the complete combustion of the combustible gas from the refined syngas is 20-50% of the heat produced by the complete combustion of the domestic waste.
13. The method according to claim 9 or 10, wherein the mass ratio of the water vapor to the domestic waste in the gasification melting step is 0.5-3.0.
14. The method according to claim 9 or 10, wherein the ratio of the amount of oxygen in the gasification melting step to the chemical oxygen demand of the domestic waste is 0.1-0.4.
15. The method according to claim 9 or 10, wherein the transition metal-surface-loaded absorbent is a transition metal-surface-loaded calcium carbonate ore.
16. The process according to claim 15, wherein the calcium carbonate ore is one or more selected from the group consisting of limestone, calcite and aragonite, the transition metal is nickel, copper, cobalt and/or iron, and the loading of the transition metal is 1-10% of the calcium carbonate ore.
17. The process as claimed in claim 9 or 10, wherein the contacting of the raw synthesis gas with the absorbent is carried out at a temperature of 500-700 ℃.
18. The process as claimed in claim 9 or 10, wherein the pyrolysis of the absorbent is carried out at a temperature of 850-1000 ℃.
19. The method according to claim 9 or 10, further comprising feeding fresh absorbent to the absorbent regeneration step.
20. The method of claim 9 or 10, further comprising the step of crushing the domestic waste prior to the step of gasification melting.
21. The method of claim 9 or 10, wherein the dry hydrogen-rich syngas comprises H2CO and methane, wherein H2The volume content of (A) is 70-90%, the volume content of CO is 5-20%, and the volume content of methane is 5-10%.
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Application publication date: 20210525 |