CN114574250B - Method and device for preparing clean synthetic gas by biomass chemical chain gasification - Google Patents
Method and device for preparing clean synthetic gas by biomass chemical chain gasification Download PDFInfo
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- CN114574250B CN114574250B CN202210388499.2A CN202210388499A CN114574250B CN 114574250 B CN114574250 B CN 114574250B CN 202210388499 A CN202210388499 A CN 202210388499A CN 114574250 B CN114574250 B CN 114574250B
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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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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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
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method and a device for preparing clean synthetic gas by biomass chemical chain gasification, wherein the method comprises the steps of heating and oxidizing biomass in a moving bed fuel reactor by using a circulating solid heat carrier serving as an oxygen carrier to carry out gasification reaction, so as to generate a gaseous product, semicoke and a reduced oxygen carrier; wherein the gaseous product is subjected to tar carbon dioxide reforming reaction in a moving bed reforming reactor by using a circulating solid heat carrier serving as a tar carbon dioxide reforming catalyst, so as to obtain clean synthesis gas. The invention utilizes the double-circulation oxygen carrier and the tar carbon dioxide reforming catalyst to realize the in-situ high-efficiency removal of tar, carbon dioxide and dust in biomass gasification and gaseous products thereof, and simultaneously converts the tar and the carbon dioxide into hydrogen and carbon monoxide, thereby improving the yield and the quality of synthesis gas, remarkably improving the utilization rate of atoms and energy, and avoiding the contact and the mutual pollution between the oxygen carrier and the tar carbon dioxide reforming catalyst by independent double-circulation operation.
Description
Technical Field
The invention belongs to the technical field of energy and chemical industry, and relates to a method and a device for preparing clean synthetic gas by biomass chemical chain gasification.
Background
Biomass is rich in yield, neutral in carbon and environment-friendly, and is the only renewable carbon-containing organic energy at present. Efficient clean conversion of biomass is an important way to solve the increasingly serious crisis of fossil energy and to improve the ecological environment, wherein biomass gasification technology is considered as the most promising conversion mode for producing high-quality synthesis gas by replacing fossil energy. The main components of the synthesis gas are hydrogen and carbon monoxide, which can be directly used as fuel gas for heating or generating electricity, and can be converted into liquid fuel or high-added-value chemicals through Fischer-Tropsch synthesis, and pure hydrogen is produced after separation and purification. Compared with the traditional fixed bed, fluidized bed and entrained flow gasification technology, chemical chain gasification is to decompose the gasification process into oxidation and reduction reactions, which are respectively carried out in two independent reactors or reaction spaces, and lattice oxygen of an oxygen carrier is used for replacing oxygen to circulate among the reactors and transfer heat. However, the biomass gasification process can be accompanied by the generation of a large amount of tar byproducts, so that pipelines are corroded and blocked, continuous operation of the gasification device is affected, and the efficiency of the gasification process is reduced. In addition, the gas-solid oxidation reaction between the oxygen carrier and the gaseous product in the chemical chain gasification process is easier to occur than the solid-solid oxidation reaction between the oxygen carrier and the biomass, so that the oxygen carrier preferentially oxidizes the hydrogen and the carbon monoxide in the gaseous product, the yield of the synthesis gas is reduced, the carbon dioxide content in the composition of the synthesis gas is increased, and the quality is poor, so that the method is not suitable for downstream application.
Aiming at the problem of high tar and carbon dioxide content in the biomass gasification process, patent CN107057797A discloses a composite oxygen carrier, a preparation method and application thereof in solid fuel gasification, wherein the application method comprises the steps of carrying out gasification reaction on solid fuel under the combined action of an oxidation state composite oxygen carrier and water vapor in a fuel reactor; the crude synthesis gas generated by gasification reaction enters an absorption reactor, and carbon dioxide in the crude synthesis gas is absorbed by calcium oxide to obtain high-quality synthesis gas; the reduced composite oxygen carrier and semi-coke which is not completely gasified in the fuel reactor enter an air reactor, wherein the semi-coke and the introduced hot air undergo combustion reaction, and the reduced oxygen carrier is oxidized and regenerated by the hot air and is heated by high-temperature flue gas generated by combustion; after being separated by a gas-solid separator, the oxidized oxygen carrier returns to the fuel reactor; the calcium oxide absorbing carbon dioxide enters a calcination reactor, is heated and lifted by hot flue gas from an air reactor, and is calcined and regenerated in the lifting process; the regenerated calcium oxide is separated by a gas-solid separator and then returned to the absorption reactor. The method has the following defects: the calcium oxide is utilized to absorb carbon dioxide in the gaseous product, although the concentration of the carbon dioxide is reduced, the quality of the synthesis gas is improved, a certain carbon loss is caused, the yield of the synthesis gas and the content of carbon monoxide are reduced, and tar is not fully converted; in addition, both the air reactor and the calcination reactor operate with fast fluidized beds, which have short residence times for gases and solids, resulting in inadequate regeneration of the reduced oxygen carrier and the carbon dioxide-absorbing calcium oxide and also difficulty in heating to the desired temperature.
Patent CN110982558B discloses a method for directly producing hydrogen and carbon monoxide by gasifying biomass based on chemical chain technology, which comprises, in a fluidized bed fuel reactor, gasifying biomass under the action of a calcium oxide oxygen carrier loaded with iron or nickel and steam and absorbing carbon dioxide in gaseous products by using calcium oxide to produce high-purity hydrogen; the reacted oxygen carrier and semi-coke which is not completely gasified are separated by a gas-solid separator and then enter an oxygen reactor, the semi-coke and the introduced oxygen are subjected to partial oxidation reaction to generate carbon monoxide, meanwhile, reaction heat is released to decompose calcium carbonate into calcium oxide and carbon dioxide, and the generated carbon dioxide is reacted with the semi-coke to generate carbon monoxide. The method reacts carbon dioxide with semicoke, so that the concentration of carbon dioxide in the synthesis gas can be reduced, the quality of the synthesis gas can be improved, and the carbon monoxide content in the synthesis gas can be increased. However, the following disadvantages also exist: the fuel reactor and the oxygen reactor are operated by fluidized beds, the defect of short gas residence time can cause insufficient tar conversion generated in the fuel reactor, and unconverted tar is easy to condense in a gas-solid separation device, so that the stable operation of the system is affected; in addition, the gas-solid contact time between carbon dioxide and semicoke in the oxidation reactor is short, so that the carbon dioxide is difficult to fully convert.
Disclosure of Invention
Aiming at the problems that the conversion of tar and carbon dioxide is insufficient, the yield and the quality of the synthesis gas are difficult to be compatible, the regeneration of an oxygen carrier is insufficient and the like in the biomass chemical chain gasification process, the invention provides a method and a device for preparing clean synthesis gas by biomass chemical chain gasification.
The technical scheme of the invention is as follows:
a method for preparing clean synthetic gas by biomass chemical-looping gasification, which comprises the following steps: in a moving bed fuel reactor (1), biomass is subjected to pyrolysis reaction and gasification reaction under the heating and oxidization actions of an oxidation state oxygen carrier from an oxygen carrier bin (5) to generate gaseous products, semicoke and a reduction state oxygen carrier, and the temperature of the moving bed fuel reactor (1) is 800-900 ℃; the generated gaseous product enters a moving bed reforming reactor (2) through a shutter (1 a), tar and carbon dioxide in the gaseous product are subjected to tar carbon dioxide reforming reaction under the heating and catalytic action of a catalyst from a regenerator (8), dust in the gaseous product is captured by a moving particle bed formed by the catalyst, the obtained clean synthetic gas is led out from a gas channel (2 b) through the shutter (2 a), and the temperature of the moving bed reforming reactor (2) is 750-850 ℃; semicoke and a reduced oxygen carrier in the moving bed fuel reactor (1) enter a combustion section (3 a) at the lower part of the riser air reactor (3), the reduced oxygen carrier is oxidized into an oxidized oxygen carrier by the introduced hot air, the semicoke is burnt out by the hot air to generate ash and hot flue gas, the oxidized oxygen carrier is heated by the heat released by combustion, then the oxidized oxygen carrier and the ash enter a lifting section (3 b) at the upper part of the riser air reactor (3) and are lifted to a gas-solid separator (4) by the hot flue gas and the introduced hot air, and the inlet temperature of the hot air is higher than 300 ℃; the dust-containing flue gas and the oxidation state oxygen carrier are separated in a gas-solid separator (4), wherein the dust-containing flue gas is discharged after dust removal and heat recovery, the oxidation state oxygen carrier enters an oxygen carrier bin (5), and then returns to the moving bed fuel reactor (1) to form a circulation loop; the carbon deposition catalyst in the moving bed reforming reactor (2) with dust trapped therein enters a lifter (6) and is lifted to a gas-solid separator (7) by air; the dust-containing tail gas and the carbon deposition catalyst are separated in a gas-solid separator (7), wherein the dust-containing tail gas is discharged after dust removal, the carbon deposition catalyst enters a regenerator (8) and is burnt and regenerated with the introduced hot air and auxiliary fuel, and the heat released by the combustion heats the regenerated catalyst and then returns to a reaction chamber of the moving bed reforming reactor (2) to form a circulation loop.
The moving bed fuel reactor (1) is connected with the moving bed reforming reactor (2) through a baffle plate with a shutter (1 a) arranged at the upper part, and the shutter (1 a) is higher than a particle bed layer in the moving bed fuel reactor (1); the right side of the moving bed reforming reactor (2) is provided with a baffle plate with a shutter (2 a) at the lower part, so that the parallel flow and cross flow contact of gaseous products and a moving particle bed layer are formed, and clean synthetic gas is led out. The fuel reactor adopts a moving bed operation mode, which is beneficial to solid-solid contact and reaction of biomass and an oxygen carrier. The reforming reactor adopts a moving bed operation mode, is favorable for full contact of tar and a catalyst, prolongs the contact time of the tar and the catalyst, ensures more full tar conversion, and can also utilize a formed movable particle bed layer to trap dust in gaseous products.
The top of the combustion section (3 a) of the riser air reactor (3) is communicated with the bottom of the lifting section (3 b); the combustion section (3 a) is a dense-phase fluidized bed to provide enough gas and solid residence time for full combustion of semicoke and full heating of the oxidation state oxygen carrier by utilizing heat released by combustion; the lifting section (3 b) is a dilute phase conveying bed and is used for lifting the oxidation state oxygen carrier and continuously heating the oxidation state oxygen carrier by utilizing hot flue gas in the lifting process; the flow cross-sectional area of the combustion section (3 a) is larger than the flow cross-sectional area of the lifting section (3 b).
The biomass is one or a mixture of more of agricultural waste, forestry waste, energy crops and wood chips; the particle size of the biomass is 0.1-3mm.
The oxygen carrier is one or two of copper-based oxygen carrier, iron-based oxygen carrier and nickel-based oxygen carrier, and the particle size of the oxygen carrier is 0.1-0.8mm; the catalyst is a tar carbon dioxide reforming catalyst, which is a nickel-calcium-based composite oxide catalyst or a nickel-magnesium-based composite oxide catalyst or a nickel-cerium-based composite oxide catalyst, and the particle size of the tar carbon dioxide reforming catalyst is 0.4-0.8mm.
Controlling the temperature of the moving bed fuel reactor (1) by controlling the temperature of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) and the ratio of the circulation rate of the oxidation state oxygen carrier to the biomass feeding rate, wherein the temperature of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) is 900-950 ℃, and the ratio of the circulation rate of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) to the biomass feeding rate is 15-50:1.
when the combustion in the riser air reactor (3) is insufficient to heat the oxygen carrier in oxidation state to a temperature at which it enters the moving bed fuel reactor (1), the heat is supplemented by the combustion of the auxiliary fuel by adding the auxiliary fuel in the combustion section (3 a) at the bottom of the riser air reactor (3).
The temperature of the moving bed reforming reactor (2) is controlled by controlling the temperature of the catalyst entering the moving bed reforming reactor (2) and the ratio of the catalyst circulation rate to the biomass feed rate, wherein the temperature of the catalyst entering the moving bed reforming reactor (2) is 850-900 ℃, and the ratio of the catalyst circulation rate to the biomass feed rate entering the moving bed reforming reactor (2) is 10-50:1.
fresh oxygen carriers and catalyst inlets are respectively arranged at the lower part of the riser air reactor and the lower part of the riser so as to supplement the abrasion and loss of the oxygen carriers and the catalyst.
The invention also provides a device for preparing clean synthetic gas by biomass chemical chain gasification, which comprises the following steps:
the moving bed fuel reactor (1) is used for carrying out pyrolysis reaction and gasification reaction on biomass to generate gaseous products, semicoke and a reduced oxygen carrier;
the moving bed reforming reactor (2), the moving bed reforming reactor (2) is communicated with the moving bed fuel reactor (1) through a first louver (1 a), and the gaseous product enters the moving bed reforming reactor through the first louver (1 a) to carry out tar carbon dioxide reforming reaction and adsorption dust removal to obtain clean synthetic gas;
the first circulation loop comprises a riser air reactor (3), wherein the moving bed fuel reactor (1) is communicated with the riser air reactor (3) through a combustion section (3 a) at the lower part of the riser air reactor (3), and a lifting section (3 b) at the upper part of the riser air reactor (3) is connected with a first gas-solid separator (4); the first gas-solid separator (4) is connected with the moving bed fuel reactor (1) through an oxygen carrier bin (5);
a second circulation loop comprising a lifter (6), wherein the lifter (6) is connected to the moving bed reforming reactor (2) and is used for introducing the carbon deposition catalyst with captured dust into the lifter (6) to be lifted to a second gas-solid separator (7) by air; the second gas-solid separator (7) is connected with the moving bed reforming reactor (2) through a regenerator (8).
Optionally, the system further comprises a second louver (2 a), wherein the second louver (2 a) is arranged in the moving bed reforming reactor (2), and clean synthesis gas is led out through the second louver (2 a).
Optionally, the oxygen carrier and the catalyst inlet are respectively arranged at the lower part of the riser air reactor (3) and the lower part of the riser (6) so as to supplement the abrasion and the loss of the oxygen carrier and the catalyst.
Optionally, the first gas-solid separator (4) discharges dust-containing flue gas, and the second gas-solid separator (7) discharges dust-containing tail gas.
The invention has the beneficial effects that:
(1) By utilizing the dual-cycle oxygen carrier and the tar carbon dioxide reforming catalyst, the in-situ efficient removal of tar, carbon dioxide and dust in biomass gasification and gaseous products thereof is realized, meanwhile, the tar and the carbon dioxide are converted into hydrogen and carbon monoxide, the yield and the quality of the synthesis gas are improved, and the atomic and energy utilization rate is remarkably improved.
(2) By utilizing independent double-circulation operation, the biomass gasification, the tar carbon dioxide reforming and the independent optimization and regulation of the oxygen carrier and the catalyst regeneration process can be respectively realized, and the contact and the mutual pollution between the oxygen carrier and the tar carbon dioxide reforming catalyst are avoided.
(3) The in-situ tar and carbon dioxide removal avoids the subsequent condensation purification unit, and can utilize sensible heat in the gaseous product to be directly in butt joint with a downstream unit, thereby shortening the process flow of preparing the synthetic gas by biomass chemical chain gasification, reducing the equipment cost and improving the comprehensive energy utilization efficiency.
(4) The contact mode of the gas-solid parallel flow and the cross flow in the moving bed reforming reaction is beneficial to the full contact of tar and carbon dioxide with the tar carbon dioxide reforming catalyst, and realizes the efficient conversion of the tar and the carbon dioxide.
(5) The lower part of the riser air reactor is provided with a dense-phase fluidized bed combustion section, so that sufficient residence time of gas and solid is provided to enable semicoke to be fully combusted and an oxidation state oxygen carrier to be heated to a required temperature, and the defect of short residence time of gas and solid in the traditional riser reactor is overcome.
Drawings
FIG. 1 is a process flow diagram of clean syngas production by chemical looping gasification of biomass in accordance with one embodiment of the invention.
In the figure: a moving bed fuel reactor; 1a shutter; 2a moving bed reforming reactor; 2a blinds; 2b gap; 3a riser air reactor; 3a combustion section; 3b lifting section; 4, a first gas-solid separator; 5 oxygen carrier bin; 6, a lifter; 7, a second gas-solid separator; 8 regenerators.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art.
Example 1
As shown in fig. 1: the embodiment provides a method for preparing clean synthetic gas by biomass chemical looping gasification, which comprises the following steps:
in the moving bed fuel reactor (1), biomass is subjected to pyrolysis reaction and gasification reaction under the heating and oxidization action of an oxidation state oxygen carrier from an oxygen carrier bin (5) to generate gaseous products, semicoke and a reduction state oxygen carrier;
the gaseous product enters a moving bed reforming reactor (2), tar and carbon dioxide in the gaseous product are subjected to tar carbon dioxide reforming reaction under the heating and catalytic action of a catalyst from a regenerator (8), and meanwhile, dust in the gaseous product is captured by a moving particle bed formed by the catalyst, so that the obtained clean synthesis gas is led out from a gas channel (2 b);
wherein, the liquid crystal display device comprises a liquid crystal display device,
semicoke and a reduced oxygen carrier in the moving bed fuel reactor (1) enter a combustion section (3 a) at the lower part of the riser air reactor (3), the reduced oxygen carrier is oxidized into an oxidized oxygen carrier by the introduced hot air, the semicoke is burnt out by the hot air to generate ash and hot flue gas, the oxidized oxygen carrier is heated by heat released by combustion, and then the oxidized oxygen carrier and the ash enter a lifting section (3 b) at the upper part of the riser air reactor (3) and are lifted to a gas-solid separator (4) by the hot flue gas and the introduced hot air; the dust-containing flue gas and the oxidation state oxygen carrier are separated in a first gas-solid separator (4), wherein the dust-containing flue gas is discharged after dust removal and heat recovery, the oxidation state oxygen carrier enters an oxygen carrier bin (5) and then returns to the moving bed fuel reactor (1) to form a first circulation loop;
the carbon deposition catalyst in the moving bed reforming reactor (2) with captured dust enters a lifter (6) and is lifted to a second gas-solid separator (7) by air; the dust-containing tail gas and the carbon deposition catalyst are separated in a second gas-solid separator (7), wherein the dust-containing tail gas is discharged after dust removal, the carbon deposition catalyst enters a regenerator (8) to be burnt and regenerated with the introduced hot air and auxiliary fuel, and the heat released by the burning heats the regenerated catalyst and then returns to a reaction chamber of the moving bed reforming reactor (2) to form a second circulation loop.
Wherein the biomass is one or a mixture of more of agricultural waste, forestry waste, energy crops and wood chips; and/or the biomass has a particle size of 0.1-3mm.
Optionally, the oxygen carrier is one or two of a copper-based oxygen carrier, an iron-based oxygen carrier and a nickel-based oxygen carrier; and/or the particle size of the oxygen carrier is 0.1-0.8mm; and/or the catalyst is a tar carbon dioxide reforming catalyst;
preferably, the catalyst is a nickel-calcium-based composite oxide catalyst or a nickel-magnesium-based composite oxide catalyst or a nickel-cerium-based composite oxide catalyst;
preferably, the tar carbon dioxide reforming catalyst has a particle size of 0.4-0.8mm.
Optionally, controlling the temperature of the moving bed fuel reactor (1) by controlling the temperature of the oxidized oxygen carrier entering the moving bed fuel reactor (1) and the ratio of the oxidized oxygen carrier circulation rate to the biomass feed rate;
optionally, wherein the temperature of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) is 900-950 ℃, and the ratio of the circulation rate of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) to the biomass feed rate is (15-50): 1.
optionally, the method further comprises:
when the combustion in the riser air reactor (3) is insufficient to heat the oxygen carrier in oxidation state to a temperature at which it enters the moving bed fuel reactor (1), the heat is supplemented by the combustion of the auxiliary fuel by adding the auxiliary fuel in the combustion section (3 a) at the bottom of the riser air reactor (3).
Optionally, further comprising controlling the temperature of the moving bed reforming reactor (2) by controlling the temperature of the catalyst entering the moving bed reforming reactor (2) and the ratio of catalyst circulation rate to biomass feed rate;
preferably, wherein the temperature of the catalyst entering the moving bed reforming reactor (2) is 850-900 ℃, and the ratio of the circulation rate of the catalyst entering the moving bed reforming reactor (2) to the biomass feed rate is (10-50): 1.
specifically, the disclosure provides a method for preparing clean synthetic gas by biomass chemical chain gasification, which adopts pine wood scraps as biomass raw materials in experiments. Before the experiment, the raw materials are crushed and screened to an average particle size of 0.38-0.83 mm, and dried for 3 hours at the temperature of 105-110 ℃ in an oven. The industrial and elemental analysis of pine wood chips are shown in table 1.
TABLE 1 Industrial and elemental analysis of pine wood chips
(bydifferential subtraction)
The oxygen carrier is CuO/olivine, wherein the theoretical loading of CuO is 10%. The preparation method comprises the following steps: crushing olivine, sieving to obtain particles with average particle size of 0.15-0.25 mm, and placing in a muffle furnace 900 o C, calcining for 4 hours. Placing the calcined olivine in Cu (NO) 3 ) 2 ·3H 2 Soaking in O solution for 24 hr, and finally placing in muffle furnace 900 o And C, roasting for 4 hours.
The tar reforming catalyst is a NiO-CaO/olivine composite oxide catalyst, wherein the total loading amount of NiO and CaO in the catalyst is 5%, and the molar ratio of NiO to CaO is 3:1. The preparation method comprises the following steps: ni (NO) with a certain concentration is firstly prepared 3 ) 2 ·6H 2 O and Ca (NO) 3 ) 2 ·4H 2 O mixed aqueous solution. Weigh a certain amount 900 o And C, calcining olivine particles with the granularity range of 0.38-0.83 mm, and soaking the olivine particles in the solution at normal temperature for 12 h. Then at rotary evaporator 90 o Distilling under reduced pressure under the condition of C to remove residual water, and then drying in a drying oven 105-110 o C drying 12 h, finally in a muffle furnace 900 o Roasting 4h under the atmosphere of C air.
As shown in fig. 1, cuO/olivine oxygen carrier was added to the oxygen carrier silo (5) at first, and NiO-CaO/olivine tar carbon dioxide reforming catalyst was added to the regenerator (8) at about 5 kg; the catalyst is, for example, a nickel-calcium-based composite oxide catalyst or a nickel-magnesium-based composite oxide catalyst or a nickel-cerium-basedComposite oxide catalysts. The air flow rate of the combustion section (3 a) at the lower part of the riser air reactor (3) is regulated to be about 2.2-2.5 m 3 And/h, the air flow rate of the lifting section (3 b) is about 4.0-4.2 m 3 And/h. The ratio of the circulation rate of the oxygen carrier to the feed rate into the moving bed fuel reactor (1) was 12, at which time the temperature of the moving bed fuel reactor (1) was 800 o C. The ratio of the circulation rate of the tar carbon dioxide reforming catalyst to the feed rate of the catalyst entering the moving bed reforming reactor (2) was 10, at which time the temperature of the moving bed reforming reactor (2) was 800 o C. Biomass is fed into the moving bed fuel reactor (1) at a feed rate of 0.22 kg/h by a two-stage screw feeder and is heated and oxidized by a high temperature oxidation state oxygen carrier from an oxygen carrier silo (5) to undergo pyrolysis and gasification reactions. The generated gaseous product enters the moving bed reforming reactor (2) through a first shutter gas channel at the upper part of the partition plate, and is contacted with a moving particle bed formed by a catalyst descending from the regenerator (8) in parallel flow and cross flow, tar and carbon dioxide in the gaseous product are converted into hydrogen and carbon monoxide under the catalysis of a tar carbon dioxide reforming catalyst, and dust carried in the gaseous product is captured by the moving particle bed. The obtained clean synthesis gas is led out from a second shutter gas channel at the lower part of a baffle plate at the right side of the moving bed reforming reactor (2), wherein condensable components in the gas are captured by a condensing system and collected in a tar storage tank, and non-condensable components are collected in a gas holder after passing through a condensing cooler. The reduced oxygen carrier and semicoke leaving the moving bed fuel reactor (1) enter a combustion section (3 a) at the lower part of the riser air reactor (3), the semicoke is burnt out and releases heat by the introduced hot air, and the reduced oxygen carrier is oxidized by the hot air and heated to 900 o C, then enters a lifting section (3 b) and is lifted to a first gas-solid separator (4) by hot air and hot flue gas. The dust-trapped carbon catalyst leaving the moving bed reforming reactor enters a lifter (6) and is lifted by air to a second gas-solid separator (7). The separated carbon deposition catalyst enters a regenerator, is burnt with the introduced hot air for regeneration and is heated to 850 DEG C o C. The inlet temperature of the hot air was 400 o C. Wherein, the firstThe gas-solid separator (4) and the second gas-solid separator (7) are cyclone separators.
The wood chip gasification performance under the action of different beds is shown in table 2. Experimental results show that when the CuO/olivine oxygen carrier is a circulating solid heat carrier, the contents of tar, methane and carbon dioxide in the produced gas composition are higher, and the quality of the synthetic gas is poor. When the CuO/olivine oxygen carrier and the NiO-CaO/olivine tar carbon dioxide reforming catalyst are adopted, the gas yield and the cold gas efficiency are increased, the tar, methane and carbon dioxide content in the produced gas composition is obviously reduced, and the hydrogen and carbon monoxide content is increased. No significant amount of dust was detected in the collected liquid product.
TABLE 2 comparison of pine wood chip gasification performance under different bed materials
Example 2
As shown in fig. 1, the present disclosure further provides a device for producing clean syngas by chemical looping gasification of biomass, which corresponds to the method disclosed in embodiment 1, and the same parts will not be repeated.
The device comprises:
the moving bed fuel reactor (1) is used for carrying out pyrolysis reaction and gasification reaction on biomass to generate gaseous products, semicoke and a reduced oxygen carrier; wherein the biomass is one or a mixture of several of agricultural waste, forestry waste, energy crops and wood chips; the particle size of the biomass is 0.1-3mm.
The movable bed reforming reactor (2), the movable bed reforming reactor (2) is separated from the movable bed fuel reactor (1) by a baffle plate with a first shutter (1 a) arranged at the upper part, and the first shutter (1 a) is higher than a particle bed layer in the movable bed fuel reactor (1); the moving bed reforming reactor (2) is communicated with the moving bed fuel reactor (1) through the first louver (1 a); a baffle plate with a second shutter (2 a) arranged at the lower part is arranged on the right side of the moving bed reforming reactor (2); the gaseous product enters the moving bed reforming reactor (2) through the first louver (1 a) to contact with the moving particle bed in parallel flow and cross flow to carry out tar carbon dioxide reforming reaction, and clean synthetic gas is led out through the second louver (2 a) after adsorption and dust removal.
The first circulation loop comprises a riser air reactor (3), the outlet of the moving bed fuel reactor (1) is communicated with the riser air reactor (3) through a combustion section (3 a) at the lower part of the riser air reactor (3), and the outlet of a lifting section (3 b) at the upper part of the riser air reactor (3) is connected with a first gas-solid separator (4); the outlet of the first gas-solid separator (4) is connected with the moving bed fuel reactor (1) through an oxygen carrier bin (5);
the second circulation loop comprises a lifter (6), the outlet of the moving bed reforming reactor (2) is connected with the lifter (6), and the carbon deposition catalyst with trapped dust enters the lifter (6) and is lifted to a second gas-solid separator (7) by air; the outlet of the second gas-solid separator (7) is connected with the moving bed reforming reactor (2) through a regenerator (8).
Optionally, the system further comprises a second louver (2 a), wherein the second louver (2 a) is arranged at the right lower end part of the moving bed reforming reactor (2), and clean synthetic gas is led out through the second louver (2 a).
Optionally, the oxygen carrier and the catalyst inlet are respectively arranged at the lower part of the riser air reactor (3) and the lower part of the riser (6) so as to supplement the abrasion and the loss of the oxygen carrier and the catalyst.
Optionally, the first gas-solid separator (4) discharges dust-containing flue gas, and the second gas-solid separator (7) discharges dust-containing tail gas.
The invention has the beneficial effects that:
(1) By utilizing the dual-cycle oxygen carrier and the tar carbon dioxide reforming catalyst, the in-situ efficient removal of tar, carbon dioxide and dust in biomass gasification and gaseous products thereof is realized, meanwhile, the tar and the carbon dioxide are converted into hydrogen and carbon monoxide, the yield and the quality of the synthesis gas are improved, and the atomic and energy utilization rate is remarkably improved.
(2) By utilizing independent double-circulation operation, the biomass gasification, the tar carbon dioxide reforming and the independent optimization and regulation of the oxygen carrier and the catalyst regeneration process can be respectively realized, and the contact and the mutual pollution between the oxygen carrier and the tar carbon dioxide reforming catalyst are avoided.
(3) The in-situ tar and carbon dioxide removal avoids the subsequent condensation purification unit, and can utilize sensible heat in the gaseous product to be directly in butt joint with a downstream unit, thereby shortening the process flow of preparing the synthetic gas by biomass chemical chain gasification, reducing the equipment cost and improving the comprehensive energy utilization efficiency.
(4) The contact mode of the gas-solid parallel flow and the cross flow in the moving bed reforming reaction is beneficial to the full contact of tar and carbon dioxide with the tar carbon dioxide reforming catalyst, and realizes the efficient conversion of the tar and the carbon dioxide.
(5) The lower part of the riser air reactor is provided with a dense-phase fluidized bed combustion section, so that sufficient residence time of gas and solid is provided to enable semicoke to be fully combusted and an oxidation state oxygen carrier to be heated to a required temperature, and the defect of short residence time of gas and solid in the traditional riser reactor is overcome.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (14)
1. A method for preparing clean synthetic gas by biomass chemical chain gasification, which is characterized by comprising the following steps:
in the moving bed fuel reactor (1), biomass is subjected to pyrolysis reaction and gasification reaction under the heating and oxidization action of an oxidation state oxygen carrier from an oxygen carrier bin (5) to generate gaseous products, semicoke and a reduction state oxygen carrier;
the method comprises the steps that gaseous products enter a moving bed reforming reactor (2) through a first louver (1 a), tar and carbon dioxide in the gaseous products are subjected to tar carbon dioxide reforming reaction under the heating and catalytic action of a catalyst from a regenerator (8), dust in the gaseous products is captured by a moving particle bed formed by the catalyst, and clean synthesis gas is led out through a second louver (2 a) and a gas channel (2 b) arranged in the moving bed reforming reactor (2);
wherein, the liquid crystal display device comprises a liquid crystal display device,
the semicoke and the reduced oxygen carrier in the moving bed fuel reactor (1) enter a combustion section (3 a) at the lower part of the riser air reactor (3), the combustion section (3 a) is a dense phase fluidized bed combustion section so as to provide enough residence time for gas and solid to fully burn the semicoke and heat the oxidized oxygen carrier to a required temperature, the reduced oxygen carrier is oxidized into the oxidized oxygen carrier by the introduced hot air, the semicoke is burnt out by the hot air to generate ash and hot flue gas, the oxidized oxygen carrier is heated by the heat released by the combustion, and then the oxidized oxygen carrier and the ash enter a lifting section (3 b) at the upper part of the riser air reactor (3) and are lifted to a first gas-solid separator (4) by the hot flue gas and the introduced hot air; the dust-containing flue gas and the oxidation state oxygen carrier are separated in a first gas-solid separator (4), wherein the dust-containing flue gas is discharged after dust removal and heat recovery, the oxidation state oxygen carrier enters an oxygen carrier bin (5) and then returns to the moving bed fuel reactor (1) to form a first circulation loop;
the carbon deposition catalyst in the moving bed reforming reactor (2) with captured dust enters a lifter (6) and is lifted to a second gas-solid separator (7) by air; the dust-containing tail gas and the carbon deposition catalyst are separated in a second gas-solid separator (7), wherein the dust-containing tail gas is discharged after dust removal, the carbon deposition catalyst enters a regenerator (8) to be burnt and regenerated with the introduced hot air and auxiliary fuel, and the heat released by the burning heats the regenerated catalyst and then returns to a reaction chamber of a moving bed reforming reactor (2) to form a second circulation loop;
the method further comprises controlling the temperature of the moving bed fuel reactor (1) by controlling the temperature of the oxidized oxygen carrier entering the moving bed fuel reactor (1) and the ratio of the oxidized oxygen carrier circulation rate to the biomass feed rate.
2. The method for producing clean syngas by chemical chain gasification of biomass according to claim 1, wherein the biomass is an energy crop.
3. The method for producing clean syngas by chemical chain gasification of biomass according to claim 2, wherein the biomass is agricultural waste or forestry waste.
4. The method for producing clean syngas by chemical chain gasification of biomass according to claim 1, wherein the particle size of the biomass is 0.1-3mm.
5. The method for producing clean syngas by biomass chemical chain gasification according to claim 1, wherein the oxygen carrier is one or two of copper-based oxygen carriers, iron-based oxygen carriers, and nickel-based oxygen carriers; and/or the catalyst is a tar carbon dioxide reforming catalyst.
6. The method for producing clean syngas by chemical chain gasification of biomass according to claim 5, wherein the catalyst is a nickel-calcium-based composite oxide catalyst or a nickel-magnesium-based composite oxide catalyst or a nickel-cerium-based composite oxide catalyst.
7. The method for producing clean syngas by chemical looping gasification of biomass according to claim 5, wherein the particle size of the oxygen carrier is 0.1-0.8mm; the particle size of the tar carbon dioxide reforming catalyst is 0.4-0.8mm.
8. The method for preparing clean synthetic gas by chemical looping gasification of biomass according to claim 1, wherein,
wherein the temperature of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) is 900-950 ℃, and the ratio of the circulation rate of the oxidation state oxygen carrier entering the moving bed fuel reactor (1) to the biomass feed rate is (15-50): 1.
9. the method for producing clean syngas by chemical looping gasification of biomass according to claim 1, further comprising:
when the combustion in the riser air reactor (3) is insufficient to heat the oxygen carrier in oxidation state to a temperature at which it enters the moving bed fuel reactor (1), the heat is supplemented by the combustion of the auxiliary fuel by adding the auxiliary fuel in the combustion section (3 a) at the bottom of the riser air reactor (3).
10. The method of producing clean syngas by chemical chain gasification of biomass according to claim 1, further comprising controlling the temperature of the moving bed reforming reactor (2) by controlling the temperature of the catalyst entering the moving bed reforming reactor (2) and the ratio of catalyst circulation rate to biomass feed rate.
11. The method for producing clean syngas by chemical chain gasification of biomass according to claim 10, wherein the temperature of the catalyst entering the moving bed reforming reactor (2) is 850-900 ℃, and the ratio of the circulation rate of the catalyst entering the moving bed reforming reactor (2) to the feed rate of biomass is (10-50): 1.
12. a device for preparing clean synthetic gas by biomass chemical chain gasification, which is characterized by comprising:
the moving bed fuel reactor (1) is used for carrying out pyrolysis reaction and gasification reaction on biomass to generate gaseous products, semicoke and a reduced oxygen carrier;
the moving bed reforming reactor (2), the moving bed reforming reactor (2) is communicated with the moving bed fuel reactor (1) through a first louver (1 a), and the gaseous product enters the moving bed reforming reactor through the first louver (1 a) to carry out tar carbon dioxide reforming reaction and adsorption dust removal to obtain clean synthetic gas;
a first circulation loop comprising a riser air reactor (3), the combustion section (3 a) and the lifting section (3 b) of the riser air reactor each having a hot air inlet, the moving bed fuel reactor (1) being in communication with the riser air reactor (3) via the combustion section (3 a) in the lower part of the riser air reactor (3), the combustion section (3 a) being a dense-phase fluidized-bed combustion section to provide sufficient residence time for gases and solids to fully combust semicoke and heat the oxidized oxygen carrier to the desired temperature, the lifting section (3 b) in the upper part of the riser air reactor (3) being connected to a first solids separator (4) by controlling the temperature of the moving bed fuel reactor (1) by controlling the temperature of the oxidized oxygen carrier entering the moving bed fuel reactor (1) and the ratio of the oxidized oxygen carrier circulation rate to the biomass feed rate, such that the oxidized oxygen carrier and ash enter the first solids separator (4) in the upper part of the riser air reactor (3 b) are separated by the hot air entering the first solids separator (4); the first gas-solid separator (4) is connected with the moving bed fuel reactor (1) through an oxygen carrier bin (5);
a second circulation loop, wherein the second circulation loop comprises a lifter (6), the lifter (6) is connected with the moving bed reforming reactor (2), and the carbon deposition catalyst with captured dust enters the lifter (6) and is lifted to a second gas-solid separator (7) by air; the second gas-solid separator (7) is connected with the moving bed reforming reactor (2) through a regenerator (8);
the system also comprises a second louver (2 a), wherein the second louver (2 a) is arranged in the moving bed reforming reactor (2), and clean synthesis gas is led out through the second louver (2 a).
13. The apparatus for producing clean syngas by chemical chain gasification of biomass according to claim 12, further comprising oxygen carrier and catalyst inlet provided at the lower part of the riser air reactor (3) and the lower part of the riser (6), respectively, to supplement the wear and loss of oxygen carrier and catalyst.
14. The clean synthesis gas plant for chemical looping gasification of biomass according to claim 12, characterized in that said first gas-solid separator (4) discharges a dust-laden flue gas and said second gas-solid separator (7) discharges a dust-laden tail gas.
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