CN111498806A - Method for preparing high-purity hydrogen from biomass and system adopted by method - Google Patents
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Abstract
The invention belongs to the field of biomass energy, and particularly relates to a method for preparing high-purity hydrogen from biomass and a system adopted by the method, which are implemented according to the following steps: (1) feeding the biomass and the high-temperature heat carrier into a descending moving bed, and carrying out pyrolysis reaction under the action of working gas I to obtain gaseous pyrolysis volatile components and solid pyrolysis materials; (2) feeding the solid pyrolysis material and a cooling heat carrier into a circulating combustor for heating to obtain a high-temperature heat carrier; (3) and (3) feeding the gaseous pyrolysis volatile component into a plurality of catalytic reforming fixed beds connected in parallel, wherein at least one catalytic reforming fixed bed carries out reforming reaction on the gaseous pyrolysis volatile component under the gradient action of the working gas II and the graded catalyst, so as to obtain the target product, namely the high-purity hydrogen. The invention has high hydrogen yield, low tar content, low catalyst loss and low cost, and can solve the problems of difficult pressure drop control of the fixed bed layer, easy blockage of dust in the catalyst layer of the fixed bed and the like.
Description
Technical Field
The invention belongs to the field of biomass energy, and particularly relates to a method for preparing high-purity hydrogen from biomass and an adopted system thereof.
Background
Hydrogen gas is regarded as a promising new generation of clean energy because it does not generate carbon dioxide greenhouse gas during combustion and does not emit pollutant gases such as nitrogen and sulfur. Hydrogen is currently used in three major applications: the method comprises the steps of producing chemical raw materials such as methanol and ammonia gas, cracking and refining petroleum products, and gasifying and liquefying. However, hydrogen is mainly obtained by electrolyzing water to produce hydrogen and petrochemical energy to produce hydrogen, the former has large hydrogen production energy consumption and has the problem of economic level, and the latter has the problems of petrochemical energy consumption and environmental level although the cost is lower. In contrast, the hydrogen production by using biomass has the advantages of renewable, clean and green raw materials and the like, and is a key point and a hot point for research in the field of hydrogen production.
At present, the hydrogen production by biomass usually adopts a direct gasification method, a pyrolysis reforming method and a supercritical hydrolysis method. The direct gasification method needs a gasification agent, and when oxygen is taken as the gasification agent, the hydrogen yield is high, but the energy consumption for preparing pure oxygen is large; when air is used as a gasifying agent, although the cost is low, a large amount of nitrogen which is difficult to separate exists; the water vapor is used as a gasifying agent and is between oxygen and air. The pyrolysis reforming method is to reform the gas or bio-oil generated by pyrolysis into hydrogen, and the problems of the service performance and the service life of the catalyst exist in the autothermal reforming, chemical chain reforming and photocatalytic reforming. The supercritical water method utilizes the strong liquid dissolving power and gas diffusibility of water in a critical state to fully convert biomass, has high hydrogen concentration, does not have the tar problem, but has high equipment requirement.
Aiming at the problems of profit and weakness of various methods, the various methods are mainly coupled by researchThe combination of the process technology realizes the promotion of the biomass hydrogen production technology. Chinese patent 201410211019.0 discloses a method for producing hydrogen by blending gasification of sludge and biomass, which takes steam generated by higher moisture content of sludge as a hydrogen source, and biomass combustion to meet the requirements of a heat source, gasification, cracking and catalytic reforming three-stage reaction process in the whole process, thereby realizing the purposes of recycling effective components of sludge and converting biomass into high-quality hydrogen. However, the method consumes a large amount of biomass in the process of heating the sludge, and the hydrogen yield of the biomass is influenced, so that the process economy is not high. Chinese patent 201710216516.3 provides a circulating fluidized bed combustion gasification H with calcium spraying in biomass furnace2The process for preparing hydrogen by in-situ adsorption enhanced water-vapor conversion is characterized in that synthesis gas generated by a circulating fluidized bed is combined with a water-vapor conversion moving bed, a solid separator, a regenerator and a solid mixer to realize the simultaneous movement, reaction and regeneration of hydrogen production and hydrogen adsorption, and 100 percent pure hydrogen is obtained. However, the method adopts a reactor of calcium-based absorbent for enhancing gasification, and gasification endotherm and CO exist2The compatibility problem of the absorption exothermic reaction is solved, the cyclic loss of the calcium-based absorbent is not negligible, the process control is more complicated, the adopted multi-stage hydrogen extraction process is long, multiple temperature-changing operations are involved, and the energy loss is large.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing high-purity hydrogen from biomass, which has the advantages of high hydrogen yield, low tar content, low catalyst loss and low cost and can solve the problems of difficult control of pressure drop of a fixed bed layer, large possibility of blockage of dust of a catalyst layer of the fixed bed and the like.
The invention also provides a system for preparing high-purity hydrogen from biomass, which is matched with the method.
In order to solve the technical problem, the invention is realized as follows:
a method for preparing high-purity hydrogen from biomass can be implemented according to the following steps:
(1) feeding the biomass and the high-temperature heat carrier into a descending moving bed, and carrying out pyrolysis reaction under the action of working gas I to obtain gaseous pyrolysis volatile components and solid pyrolysis materials;
(2) feeding the solid pyrolysis material obtained in the step (1) and a cooling heat carrier into a circulating combustor for heating to obtain a high-temperature heat carrier;
(3) and (2) feeding the gaseous pyrolysis volatile component obtained in the step (1) into a catalytic reforming fixed bed, and carrying out reforming reaction on the gaseous pyrolysis volatile component under the gradient action of the working gas II and the graded catalyst to obtain the target product, namely the high-purity hydrogen.
As a preferable scheme, the heat carrier in the step (1) of the invention comprises natural ores, metal oxides and microporous materials; the natural ore is one or the combination of more than two of olivine, dolomite, attapulgite, iron ore, calcite or magnesite; the metal oxide is one or the combination of more than two of ferric oxide, titanium oxide, zirconium oxide or niobium oxide; the microporous material is one or the combination of more than two of ZSM molecular sieve, SAPO molecular sieve, Y-type molecular sieve, Beta molecular sieve, SSZ molecular sieve, SBA molecular sieve, MCM molecular sieve or zeolite.
Further, the working gas I in the step (1) is one or a combination of more than two of water vapor, oxygen, air, carbon dioxide, carbon monoxide or flue gas, and the flow rate is 0.1-5 m3H; the reaction temperature of the descending moving bed is 550-900 ℃; the reaction time is 1-10 seconds; the mass ratio of the biomass to the heat carrier is 1: 1-10.
Further, the reaction temperature of the circulating combustor in the step (2) is 800-1000 ℃, and the reaction time is 2-20 seconds.
Further, the working gas II in the step (3) is one or a combination of more than two of water vapor, oxygen, carbon dioxide or carbon monoxide, and the flow rate is 0.01-0.05 m3/h。
Further, the catalytic reforming fixed bed in the step (3) adopts a two-stage microwave heating mode of a first-stage catalytic cracking reforming section and a second-stage conversion absorption section, when a gas catalytic reforming reaction process is carried out, the reaction temperature of the first-stage catalytic cracking reforming section is 500-600 ℃, the reaction time is 1-10 minutes, the reaction temperature of the second-stage conversion absorption section is 650-780 ℃, and the reaction time is 1-10 minutes; when the regeneration reaction process is carried out, the regeneration temperature of the first-stage catalytic cracking reforming section is 600-700 ℃, the regeneration time is 1-10 minutes, the regeneration temperature of the second-stage conversion absorption section is 850-900 ℃, and the regeneration time is 1-10 minutes.
Furthermore, the staged catalyst in the step (3) of the invention is composed of a primary cracking reforming catalyst in a primary catalytic cracking reforming section and a secondary shift absorbent in a secondary shift absorption section; the active component of the first-stage cracking reforming catalyst comprises IVB、VB、VIB、VIIBAnd metal elements of group VIII 4-6 period; the carrier of the first-stage cracking reforming catalyst is one or the combination of more than two of silicon carbide-cordierite, silicon nitride-cordierite and foam silicon carbide; the active components of the secondary shift absorbent comprise calcium oxide and IIA group 2-6 period or IIIB, IVBOxides of metal elements of group 4 to 6 periods.
The system adopted by the method for preparing high-purity hydrogen from biomass comprises a material conveying spiral mechanism, a descending moving bed, a microwave source generator, a circulating combustor, a catalytic reforming fixed bed, a gas-solid separator I and a gas-solid separator II;
an outlet of the material conveying screw mechanism is communicated with a biomass raw material inlet in the middle area of the descending moving bed; the solid pyrolysis material and cooling heat carrier outlet at the bottom of the descending moving bed is communicated with the solid pyrolysis material and cooling heat carrier inlet at the bottom of the circulating combustor;
the high-temperature heat carrier outlet at the top of the circulating combustor is communicated with the gas-solid mixed phase inlet of the gas-solid separator II; a high-temperature heat carrier solid-phase separation outlet at the bottom of the gas-solid separator II is communicated with a solid-phase inlet at the upper part of the descending moving bed;
the catalytic reforming fixed bed is arranged in a microwave source generator; the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed is communicated with the gas phase outlet of the gas-solid separator I; a gas-solid mixed phase outlet of the descending moving bed is communicated with a gas-solid mixed phase separation inlet of the gas-solid separator I; the bottom solid phase separation outlet of the gas-solid separator I is communicated with the top of the descending moving bed;
the bottom of the descending moving bed is provided with a working gas I inlet; and a working gas II inlet is formed at the bottom of the catalytic reforming fixed bed.
As a preferred scheme, the descending moving bed adopts a falling type solid-solid co-current reactor; the circulating combustor adopts a portable moving bed; the catalytic reforming fixed bed adopts a vertical reactor.
Furthermore, the catalytic reforming fixed bed adopts a plurality of groups of parallel structures; the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed is respectively communicated with a gas phase outlet of the gas-solid separator I through a gas path quick switching valve; and a regeneration gas inlet is formed at the bottom of the catalytic reforming fixed bed.
Compared with the prior art, the invention has the following characteristics:
1. the invention organically combines the descending fast pyrolysis moving bed with the catalytic reforming fixed bed, realizes the synchronous operation of a plurality of processes such as pyrolysis, hydrogen production and regeneration through the switching regeneration of the catalytic reforming fixed bed, and overcomes the problems that the pressure drop of the fixed bed is difficult to control and the dust of the catalytic layer of the fixed bed is large and easy to block due to the unmatched flow rate in the conventional fluidized bed gasification-fixed bed catalytic reforming.
2. The invention provides graded gradient catalysis of a reforming fixed bed aiming at the problems of high tar content, catalyst loss and the like in the process of preparing hydrogen from biomass, realizes the removal of tar carried by pyrolysis gas and water-gas shift reaction on the fixed bed through a primary cracking reforming catalyst and a secondary shift absorbent, obtains a high-quality hydrogen product, and simultaneously overcomes the problem of mechanical wear of a calcium-based absorbent in a conventional fluidized bed.
3. Aiming at the problem of difficult matching of the biomass thermal desorption heat and carbon dioxide absorption exothermic reaction processes, the invention decouples the pyrolysis reaction and the carbon dioxide absorption reaction, realizes respective control of the two reaction processes, is beneficial to enhancing the pyrolysis reaction intensity and improving the hydrogen production yield of the biomass.
Drawings
FIG. 1 is a schematic diagram of the system for preparing high-purity hydrogen from biomass according to the present invention.
In the figure: 1. a material conveying screw mechanism; 2. a descending moving bed; 3. a gas-solid separator I; 4. a circulating combustor; 5. a gas-solid separator II; 6. a fixed catalytic reforming bed; 7. a first-stage cracking reforming catalysis section; 8. a second-order shift absorption section; 9. a microwave source generator; 10. gas circuit fast switch valve.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
As shown in fig. 1, a method for preparing high-purity hydrogen from biomass comprises the following steps:
(1) feeding the biomass and the high-temperature heat carrier into a descending moving bed, and carrying out pyrolysis reaction under the action of working gas I to obtain gaseous pyrolysis volatile components and solid pyrolysis materials;
(2) feeding the solid pyrolysis material obtained in the step (1) and a cooling heat carrier into a circulating combustor for heating to obtain a high-temperature heat carrier;
(3) and (2) feeding the gaseous pyrolysis volatile component obtained in the step (1) into a plurality of catalytic reforming fixed beds connected in parallel, wherein at least one catalytic reforming fixed bed carries out reforming reaction on the gaseous pyrolysis volatile component under the gradient action of the working gas II and the grading catalyst, so as to obtain the target product, namely the high-purity hydrogen.
The heat carrier in the step (1) is a substance with excellent heat conduction, wear resistance and catalytic activity, and comprises three major types of natural ore, metal oxide and microporous material, wherein the natural ore is one or a combination of more of olivine, dolomite, attapulgite, iron ore, calcite, magnesite and the like; the metal oxide is one or the combination of more than two of ferric oxide, titanium oxide, zirconium oxide and niobium oxide; the other materials are one or a combination of more of ZSM molecular sieve, SAPO molecular sieve, Y-type molecular sieve, Beta molecular sieve, SSZ molecular sieve, SBA molecular sieve, MCM molecular sieve and zeolite; preferably olivine; the granularity of the heat carrier is 0.05-2 mm.
The working gas I in the step (1) is one or a combination of more of water vapor, oxygen, air, carbon dioxide, carbon monoxide, flue gas and the like; preferably, the volume ratio of the water vapor to the oxygen is 1: 0.1-1; the flow rate is 0.1-5 m3/h。
The biomass raw material in the step (1) can be derived from any substance containing lignocellulose, such as corn straws, rice husks, wheat straws, wood blocks, leaves or branches, and the like, can also be derived from substances containing sugar, protein, grease and the like, such as seaweed, microalgae, duckweed and the like, and can also be derived from activated sludge, oil sludge and other organic wastes containing microorganisms; the maximum dimension of the raw materials in the direction is not more than 5mm, and preferably 0.2-2 mm.
The reaction temperature of the descending moving bed in the step (1) is 550-900 ℃; the reaction time is 1-10 seconds; the mass ratio of the biomass to the heat carrier is 1: 1-10; the pyrolysis product of the biomass is a gaseous pyrolysis volatile component and a solid pyrolysis material, wherein the solid pyrolysis material is biological semicoke, and the mass percentage of the gaseous pyrolysis volatile component accounts for 60-85 wt%, and the mass percentage of the biological semicoke is 15-40 wt%; the content of non-condensable gas in the gaseous pyrolysis volatile component reaches more than 98 percent.
The reaction temperature of the circulating combustor in the step (2) is 800-1000 ℃, and the reaction time is 2-20 seconds.
The working gas II in the step (3) is one or the combination of more than two of water vapor, oxygen, carbon dioxide, carbon monoxide and the like; preferably water vapor; the flow rate is 0.01-0.05 m3/h。
The catalytic reforming fixed bed in the step (3) of the invention adopts a two-stage microwave heating mode, and when the fixed bed carries out a gas catalytic reforming reaction process, the first-stage catalytic reforming reaction is carried outThe reaction temperature of the pyrolysis reforming section is 500-600 ℃, the reaction time is 1-10 minutes, and the microwave power density is 0.5 × 105～2×105W/m3The reaction temperature of the secondary conversion absorption section is 650-780 ℃, the reaction time is 1-10 minutes, and the microwave power density is 0.5 × 105～5×105W/m3When the fixed bed is used for the regeneration reaction process, the regeneration temperature of the first-stage catalytic cracking reforming section is 600-700 ℃, the regeneration time is 1-10 minutes, and the microwave power density is 1 × 105～5×105W/m3The regeneration temperature of the secondary conversion absorption section is 850-900 ℃, the regeneration time is 1-10 minutes, and the microwave power density is 1 × 105～5×105W/m3(ii) a In a more optimal working scheme, the regeneration reaction process can also be introduced with regeneration gas, specifically one or a combination of several of water vapor, hydrogen, synthesis gas and fuel gas; preferably, the volume ratio of the water vapor to the hydrogen is 1: 0.01-0.1; the flow rate is 0.1-0.5 m3/h。
The high-quality hydrogen concentration of the invention can reach 95 percent at most, the carbon dioxide content is lower than 5 percent, other impurity gases are not more than 0.5 percent, tar is not detected in the gases, and the dust content is lower than 50mg/Nm3The hydrogen yield in the whole process is not lower than 0.1kg/kg dry biomass.
The grading catalyst in the step (3) consists of a first-stage cracking reforming catalyst in a first-stage catalytic cracking reforming section and a second-stage shift absorbent in a second-stage shift absorption section; the active component of the first-stage cracking reforming catalyst comprises IVB、VB、VIB、VIIBAnd metal elements of group VIII 4-6 period; the carrier of the first-stage cracking reforming catalyst is one or the combination of more than two of silicon carbide-cordierite, silicon nitride-cordierite and foam silicon carbide; the active components of the secondary shift absorbent comprise calcium oxide and IIA group 2-6 period or IIIB, IVBOxides of metal elements of group 4 to 6 periods.
The grading catalyst in the step (3) of the invention consists of a first-stage cracking reforming catalyst and a second-stage shift absorbent, wherein the first-stage cracking reforming catalyst and the second-stage shift absorbent are both integral forming preparations;
the active component of the first-stage cracking reforming catalyst comprises IVB、VB、VIB、VIIBAnd a metal element of group VIII period 4 to 6, which may be specifically one or a combination of several of iron, nickel, cobalt, molybdenum, manganese, palladium, rhodium, and the like; preferably, the mass ratio of iron, nickel and manganese is 1: 0.2-0.5: 0.01-0.05; the carrier of the first-stage cracking reforming catalyst is one or the combination of more of silicon carbide-cordierite, silicon nitride-cordierite and foam silicon carbide, preferably silicon carbide-cordierite; the binder is one or a combination of more of boehmite, montmorillonite, water glass, hydrotalcite, silica gel, cellulose, starch, polyvinyl alcohol, phenolic resin, sesbania powder, tung oil and the like; the first-stage cracking reforming catalyst comprises, by mass, 5-20% of active components, 60-80% of carriers and 5-20% of binders;
the first-stage cracking reforming catalyst is prepared by adopting an impregnation method, and the preparation steps are as follows: putting a catalyst carrier into an acid solution with the concentration of 10-30%, heating for 1-8 hours at 60-90 ℃, washing with distilled water, drying for later use, then uniformly mixing a binder and a salt solution of an active component with the concentration of 5-30%, putting the carrier subjected to acid treatment into the mixed slurry, soaking for 1-5 times, drying, roasting for 4-12 hours at 600-900 ℃, and then reducing at 400-600 ℃ in a hydrogen atmosphere to obtain a first-stage cracking reforming catalyst; the acid solution comprises one or more of inorganic protonic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and the like, and also comprises one or more of organic acids such as oxalic acid, acetic acid, formic acid, succinic acid, maleic anhydride, acrylic acid, succinic acid and the like; the salt solution of the active component comprises one or a combination of a plurality of nitrate, phosphate, carbonate, acetate, oxalate, formate and the like.
The active components of the secondary shift absorbent consist of calcium oxide and IIA group 2-6 period IIIB, IVBThe oxides of the metal elements of the group 4-6 periods are composed of, by mass, 50-80% of calcium oxide and 20-50% of other metal oxides, wherein the oxides of the other metal elements can be calcium, magnesium and zirconiumOne or more of oxides of titanium, yttrium, lanthanum, cerium and the like; the carrier of the secondary conversion absorbent is one or a combination of more of silicon carbide-cordierite, silicon nitride-cordierite and foam silicon carbide; preferably silicon carbide-cordierite; the binder is one or a combination of more of boehmite, montmorillonite, water glass, hydrotalcite, silica gel, cellulose, starch, polyvinyl alcohol, phenolic resin, sesbania powder, tung oil and the like; the secondary conversion absorbent comprises, by mass, 20-50% of active components, 40-70% of carriers and 5-20% of binders;
the second-stage transformation absorbent is prepared by adopting an impregnation method, and the preparation steps are as follows: putting a catalyst carrier into an acid solution with the concentration of 10-30%, heating for 1-8 hours at the temperature of 60-90 ℃, washing with distilled water and drying for later use, then uniformly mixing a binder and an active component salt solution with the concentration of 5-20%, putting the carrier subjected to acid treatment into the mixed slurry for soaking for 1-5 times, drying and roasting for 6-12 hours at the temperature of 850-1000 ℃ to obtain a secondary conversion absorbent; the acid solution comprises one or more of inorganic protonic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and the like, and also comprises one or more of organic acids such as oxalic acid, acetic acid, formic acid, succinic acid, maleic anhydride, acrylic acid, succinic acid and the like; the salt solution of the active component comprises one or a combination of a plurality of nitrate, phosphate, carbonate, acetate, oxalate, formate and the like.
The system adopted by the method for preparing high-purity hydrogen from biomass comprises a material conveying spiral mechanism 1, a descending moving bed 2, a microwave source generator 9, a circulating combustor 4, a catalytic reforming fixed bed 6, a gas-solid separator I3 and a gas-solid separator II 5;
an outlet of the material conveying screw mechanism 1 is communicated with a biomass raw material inlet in the middle area of the descending moving bed 2; the solid pyrolysis material and cooling heat carrier outlet at the bottom of the descending moving bed 2 is communicated with the solid pyrolysis material and cooling heat carrier inlet at the bottom of the circulating combustor 4;
the high-temperature heat carrier outlet at the top of the circulating combustor 4 is communicated with the gas-solid mixed phase inlet of the gas-solid separator II 5; a high-temperature heat carrier solid-phase separation outlet at the bottom of the gas-solid separator II5 is communicated with a solid-phase inlet at the upper part of the descending moving bed 2;
the catalytic reforming fixed bed 6 is arranged in a microwave source generator 9; the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed 6 is communicated with the gas phase outlet of the gas-solid separator I3; a gas-solid mixed phase outlet of the descending moving bed 2 is communicated with a gas-solid mixed phase separation inlet of a gas-solid separator I3; the solid phase separation outlet at the bottom of the gas-solid separator I3 is communicated with the top of the descending moving bed 2;
the bottom of the descending moving bed 2 is provided with a working gas I inlet; the bottom of the catalytic reforming fixed bed 6 is provided with a working gas II inlet.
The descending moving bed 2 adopts a falling type solid-solid co-current reactor; the circulating combustor 4 adopts a portable moving bed; the fixed catalytic reforming bed 6 adopts a vertical reactor.
The catalytic reforming fixed bed 6 adopts a multi-group parallel structure; the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed 6 is respectively communicated with a gas phase outlet of a gas-solid separator I3 through a gas path quick switching valve 10; the bottom of the catalytic reforming fixed bed 6 is provided with a regeneration gas inlet.
Referring to fig. 1, a descending moving bed 2 of the present invention is used for receiving a biomass raw material and a working gas I from a working gas I feeding line, and obtaining a gaseous pyrolysis volatile component and a solid pyrolysis material after reaction; the circulating combustor 4 is used for receiving the solid pyrolysis material and the cooling heat carrier from the descending moving bed 2, and combusting and heating the solid pyrolysis material and the cooling heat carrier in an oxidizing atmosphere to obtain a recyclable high-temperature heat carrier; the catalytic reforming fixed bed 6 comprises a plurality of catalytic reforming fixed beds connected in parallel, and is used for receiving gaseous pyrolysis volatile components (obtained after gas-solid separation by a gas-solid separator I3) from the descending moving bed 2 and working gas II from a working gas II feeding pipeline to obtain high-quality hydrogen when the catalytic reforming fixed bed 6 performs gas catalytic reforming reaction; when the catalytic reforming fixed bed 6 carries out regeneration reaction, the microwave source generator 9 heats the catalytic reforming fixed bed by microwave and receives regeneration gas from a regeneration gas feeding pipeline to realize regeneration of the catalytic reforming fixed bed; the gas-solid separator comprises a two-stage gas-solid separator, wherein the gas-solid separator I3 is used for receiving the gaseous pyrolysis volatile components from the descending moving bed 2 and obtaining a gas-phase material I and a solid pyrolysis material after separation; the gas-solid separator II is used for receiving the gas-phase material II from the circulating combustor 4 and separating to obtain a high-temperature heat carrier and flue gas.
The descending moving bed 2 is a falling solid-solid concurrent reactor, a biomass feeding spiral mechanism 1 is arranged in the middle of the reactor, a heat carrier feeding port (a high-temperature heat carrier solid-phase separation outlet) is arranged at the upper part of the reactor, a gas-solid separator I is arranged at the top of the reactor, and a working gas I inlet is arranged at the bottom of the reactor; the biomass solid-phase material falls from the material conveying screw mechanism 1 in the middle of the downward moving bed 2 by gravity, the high-temperature heat carrier enters from the heat carrier feed inlet on the upper part of the downward moving bed 2, the biomass is rapidly pyrolyzed after contacting with the high-temperature heat carrier under the action of the working gas I, the produced gaseous pyrolysis volatile matter enters the gas-solid separator I, the gaseous pyrolysis volatile matter is sent into the catalytic reforming fixed bed through gas-solid separation, and the residual solid-state pyrolysis material and the heat carrier cooled after heat exchange fall together by gravity and enter the circulating combustor 4.
The circulating combustor 4 is a portable moving bed, a cooling heat carrier feeding hole is formed in the lower portion of the circulating combustor 4, and an oxidizing gas flow inlet is formed below the cooling heat carrier feeding hole; the cooling heat carrier and the solid pyrolysis material enter the circulating combustor 4 from the bottom and are lifted upwards under the action of the oxidation airflow, the solid pyrolysis material is subjected to combustion reaction in the lifting process, and the cooling heat carrier obtains a high-temperature heat carrier through heat exchange.
The catalytic reforming fixed bed 6 is a vertical reactor, the bottom of the vertical reactor is respectively provided with a gaseous pyrolysis volatile component inlet, a working gas II inlet and a regeneration gas inlet, and the top of the reactor is provided with a hydrogen product outlet; the bed layer of the vertical reactor is divided into two layers, the lower layer is a first-stage cracking reforming catalysis section 7, and the upper layer is a second-stage conversion absorption section 8; after gaseous pyrolysis volatile components from the descending moving bed 2 enter the catalytic reforming fixed bed 6, tar cracking, hydrocarbon micromolecule reforming and other reactions are firstly carried out in a lower-layer first-stage cracking reforming catalytic section 7 to obtain synthesis gas mainly containing hydrogen, carbon monoxide and carbon dioxide, then the synthesis gas enters a second-stage conversion absorption section 8 to carry out a water vapor conversion reaction and a removal reaction of residual tar and hydrocarbon micromolecules, and finally a high-quality hydrogen product is obtained. When the reaction efficiency of the catalytic reforming fixed bed 6 is reduced, the gaseous pyrolysis volatile component inlet and the working gas II inlet are closed, the regeneration gas inlet is opened, and meanwhile, the microwave heating power density of the microwave source generator 9 is adjusted, so that the requirements of regeneration process conditions are met, and the recycling of the primary pyrolysis reforming catalyst and the secondary conversion absorbent is realized.
The catalytic reforming fixed bed is characterized in that a certain number of microwave quartz windows are respectively arranged on the wall of a reactor, each window corresponds to one microwave generator, the power of each microwave generator is 500-2000W, the specific number of the windows is set according to the volume and other conditions of the reactor, the specific number of the windows is generally 2-10, and the power density in the reactor is ensured to be 0.5 × 105～5×105W/m3。
The gas-solid separator is based on one or more of gravity settling, centrifugal separation, filter screen separation, static electricity, adsorption and the like, but is not limited to the above means, and can be one or a combination of more than two of a cyclone separator, a cloth bag filter, an electrostatic dust collector and an adsorption separator.
As shown in figure 1, the biomass raw material is conveyed to a descending moving bed 2 through a material conveying screw mechanism 1, a heat carrier falls into the descending moving bed 2 through a solid outlet (a high-temperature heat carrier solid-phase separation outlet) of a gas-solid separator II5, biomass is rapidly pyrolyzed after being contacted with the high-temperature heat carrier under the action of working gas I, generated gaseous pyrolysis volatile matter enters a gas-solid separator I3 and is conveyed to a catalytic reforming fixed bed 6 through gas-solid separation, residual solid pyrolysis material and the heat carrier cooled after heat exchange fall together by gravity into a thermal circulation combustor 4, and the high-temperature heat carrier is obtained through oxidation combustion regeneration and falls into the descending moving bed 2 again through a gas-solid separator II5 for recycling. The gaseous pyrolysis volatile matter entering the catalytic reforming fixed bed 6 firstly enters a first-stage pyrolysis reforming catalytic section 7 in the catalytic reforming fixed bed 6, tar cracking removal and small molecular hydrocarbon reforming reaction are carried out under the action of a microwave source generator 9 and working gas II, and then the gaseous pyrolysis volatile matter further enters a second-stage conversion absorption section 8 in the catalytic reforming fixed bed 6 to carry out carbon dioxide absorption reaction and removal and conversion of residual tar and small molecular hydrocarbon through the action of the microwave source generator 9 under the carrying of the working gas II, so that a high-quality hydrogen product is obtained. When the two-stage reaction efficiency of the catalytic reforming fixed bed 6 is reduced, the catalytic reforming fixed bed 6 is regenerated by opening and closing the gas path quick switching valve 10, increasing the heating power of the microwave source generator 9 and introducing regeneration gas.
Examples
a. First-order pyrolysis reforming catalyst preparation
Putting silicon carbide-cordierite into oxalic acid solution with the concentration of 20 percent, heating for 6 hours at 80 ℃, washing with distilled water and drying for later use; mixing ferric nitrate, nickel nitrate and manganese nitrate according to the mass ratio of active component metal elements of 1:0.3:0.05 to prepare a mixed solution with the concentration of 15%, then mixing boehmite and the mixed solution to form slurry, putting the silicon carbide-cordierite subjected to acid treatment into the mixed slurry to be soaked for 1-5 times, drying, roasting at 800 ℃ for 6 hours, and reducing at 400-600 ℃ in a hydrogen atmosphere to obtain a first-stage cracking reforming catalyst; the first-stage cracking reforming catalyst comprises 15% of active components containing iron, nickel and manganese, 75% of silicon carbide-cordierite and 10% of boehmite by mass percentage.
b. Preparation of second order shift absorbent
Putting silicon carbide-cordierite into oxalic acid solution with the concentration of 20 percent, heating for 6 hours at 80 ℃, washing with distilled water and drying for later use; respectively mixing calcium oxide, magnesium oxide and nitrate of zirconium oxide according to the mass percentage of 70%, 20% and 10% of metal oxide, preparing a mixed solution with the concentration of 10%, then mixing silica gel and the mixed solution to form slurry, putting the silicon carbide-cordierite subjected to acid treatment into the mixed slurry, soaking for 1-5 times, drying, and roasting for 8 hours at 900 ℃ to obtain a secondary conversion absorbent; the secondary conversion absorbent comprises, by mass, 40% of active components containing calcium oxide, magnesium oxide and zirconium oxide, 50% of silicon carbide-cordierite and 10% of silica gel.
c. Preparation of high-purity hydrogen
According to the mass ratio of biomass to heat carrier of 1:8, feeding biomass raw material and olivine high-temperature heat carrier (granularity 0.2 mm) into a descending moving bed 2 under the action of gravity, and feeding the biomass raw material and the olivine high-temperature heat carrier into a mixed gas flow of 1m of water vapor and oxygen (the volume ratio of the water vapor to the oxygen is 1: 0.1)3Obtaining gaseous pyrolysis volatile components and biological semicoke under the action of the reaction solution and the pyrolysis temperature of 800 ℃ and the pyrolysis time of 6 seconds, wherein the content of the gaseous pyrolysis volatile components is 80 percent, and the content of the biological semicoke is 20 percent; the cooled olivine high-temperature heat carrier and the biological semicoke are sent into a circulating combustor 4, and regeneration is carried out at the temperature of 900 ℃ and the reaction time of 5 seconds; the gaseous pyrolysis volatile component enters a catalytic reforming fixed bed 6, and the flow of water vapor is 0.02m3Under the action of/h, the reaction temperature is 500 ℃ in the first-stage catalytic cracking reforming section, the reaction time is 10 minutes, and the microwave power density is 0.5 × 105W/m3Performing tar cracking and hydrocarbon micromolecule reforming reaction under the condition, then entering a secondary conversion absorption section under the carrying of water vapor, reacting for 6 minutes at the reaction temperature of 720 ℃, and the microwave power density of 2 × 105W/m3Carrying out carbon dioxide absorption reaction, cracking of residual tar and reforming reaction of a small amount of hydrocarbon micromolecules under the condition to obtain a high-quality hydrogen product; the high-quality hydrogen concentration is 95%, the carbon dioxide content is 4.6%, other impurity gases are 0.4%, tar is not detected in the gases, and the dust content is 30mg/Nm3The hydrogen yield in the whole process is 0.12kg/kg dry biomass, when the reaction efficiency of the catalytic reforming fixed bed 2 is reduced, the regeneration is carried out, the regeneration temperature of the first-stage catalytic cracking reforming section is 650 ℃, the regeneration time is 5 minutes, and the microwave power density is 1 × 105The regeneration temperature of the two-stage conversion absorption section is 900 ℃, the regeneration time is 5 minutes, and the microwave power density is 2 × 105W/m3(ii) a The regeneration reaction process is introduced with regeneration gas of water vapor and hydrogen (the volume ratio of the water vapor to the hydrogen is 1: 0.05), and the flow rate is 0.4m3/h。
It should be understood that the detailed description of the present invention is only for illustrating the present invention and is not limited by the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention can be modified or substituted equally to achieve the same technical effects; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. The method for preparing high-purity hydrogen from biomass is characterized by comprising the following steps:
(1) feeding the biomass and the high-temperature heat carrier into a descending moving bed, and carrying out pyrolysis reaction under the action of working gas I to obtain gaseous pyrolysis volatile components and solid pyrolysis materials;
(2) feeding the solid pyrolysis material obtained in the step (1) and a cooling heat carrier into a circulating combustor for heating to obtain a high-temperature heat carrier;
(3) and (2) feeding the gaseous pyrolysis volatile component obtained in the step (1) into a catalytic reforming fixed bed, and carrying out reforming reaction on the gaseous pyrolysis volatile component under the gradient action of the working gas II and the graded catalyst to obtain the target product, namely the high-purity hydrogen.
2. The method for preparing high-purity hydrogen from biomass according to claim 1, characterized in that: the heat carrier in the step (1) comprises natural ore, metal oxide and microporous material; the natural ore is one or the combination of more than two of olivine, dolomite, attapulgite, iron ore, calcite or magnesite; the metal oxide is one or the combination of more than two of ferric oxide, titanium oxide, zirconium oxide or niobium oxide; the microporous material is one or the combination of more than two of ZSM molecular sieve, SAPO molecular sieve, Y-type molecular sieve, Beta molecular sieve, SSZ molecular sieve, SBA molecular sieve, MCM molecular sieve or zeolite.
3. The method for preparing high-purity hydrogen from biomass according to claim 2, characterized in that: the working gas I in the step (1) is water vapor, oxygen, air and dioxygenOne or more of carbon monoxide and flue gas with a flow rate of 0.1-5 m3H; the reaction temperature of the descending moving bed is 550-900 ℃; the reaction time is 1-10 seconds; the mass ratio of the biomass to the heat carrier is 1: 1-10.
4. The method for preparing high-purity hydrogen from biomass according to claim 3, is characterized in that: the reaction temperature of the circulating combustor in the step (2) is 800-1000 ℃, and the reaction time is 2-20 seconds.
5. The method for preparing high-purity hydrogen from biomass according to claim 4, is characterized in that: the working gas II in the step (3) is one or the combination of more than two of water vapor, oxygen, carbon dioxide or carbon monoxide, and the flow rate is 0.01-0.05 m3/h。
6. The method for preparing high-purity hydrogen from biomass according to claim 5, is characterized in that: the catalytic reforming fixed bed in the step (3) adopts a first-stage catalytic cracking reforming section and a second-stage conversion absorption section two-stage microwave heating mode, when a gas catalytic reforming reaction process is carried out, the reaction temperature of the first-stage catalytic cracking reforming section is 500-600 ℃, the reaction time is 1-10 minutes, the reaction temperature of the second-stage conversion absorption section is 650-780 ℃, and the reaction time is 1-10 minutes; when the regeneration reaction process is carried out, the regeneration temperature of the first-stage catalytic cracking reforming section is 600-700 ℃, the regeneration time is 1-10 minutes, the regeneration temperature of the second-stage conversion absorption section is 850-900 ℃, and the regeneration time is 1-10 minutes.
7. The method for preparing high-purity hydrogen from biomass according to claim 6, characterized in that: the grading catalyst in the step (3) consists of a first-stage cracking reforming catalyst in a first-stage catalytic cracking reforming section and a second-stage shift absorbent in a second-stage shift absorption section; the active component of the first-stage cracking reforming catalyst comprises IVB、VB、VIB、VIIBAnd metal elements of group VIII 4-6 period; said oneThe carrier of the stage cracking reforming catalyst is one or the combination of more than two of silicon carbide-cordierite, silicon nitride-cordierite and foam silicon carbide; the active components of the secondary shift absorbent comprise calcium oxide and IIA group 2-6 period or IIIB, IVBOxides of metal elements of group 4 to 6 periods.
8. The system adopted by the method for preparing high-purity hydrogen from biomass according to any one of claims 1 to 7 is characterized in that: comprises a material conveying screw mechanism (1), a descending moving bed (2), a microwave source generator (9), a circulating combustor (4), a catalytic reforming fixed bed (6), a gas-solid separator I (3) and a gas-solid separator II (5);
an outlet of the material conveying screw mechanism (1) is communicated with a biomass raw material inlet in the middle area of the descending moving bed (2); the solid pyrolysis material and cooling heat carrier outlet at the bottom of the descending moving bed (2) is communicated with the solid pyrolysis material and cooling heat carrier inlet at the bottom of the circulating combustor (4);
a high-temperature heat carrier outlet at the top of the circulating combustor (4) is communicated with a gas-solid mixed phase inlet of the gas-solid separator II (5); a high-temperature heat carrier solid-phase separation outlet at the bottom of the gas-solid separator II (5) is communicated with a solid-phase inlet at the upper part of the descending moving bed (2);
the catalytic reforming fixed bed (6) is arranged in a microwave source generator (9); the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed (6) is communicated with the gas phase outlet of the gas-solid separator I (3); a gas-solid mixed phase outlet of the descending moving bed (2) is communicated with a gas-solid mixed phase separation inlet of the gas-solid separator I (3); the solid phase separation outlet at the bottom of the gas-solid separator I (3) is communicated with the top of the descending moving bed (2);
the bottom of the descending moving bed (2) is provided with a working gas I inlet; and a working gas II inlet is formed at the bottom of the catalytic reforming fixed bed (6).
9. The system adopted by the method for preparing high-purity hydrogen by biomass according to claim 8 is characterized in that: the descending moving bed (2) adopts a falling type solid-solid co-current reactor; the circulating combustor (4) adopts a portable moving bed; the catalytic reforming fixed bed (6) adopts a vertical reactor.
10. The system adopted by the method for preparing high-purity hydrogen by biomass according to claim 9 is characterized in that: the catalytic reforming fixed bed (6) adopts a multi-group parallel structure; the bottom gaseous pyrolysis volatile component inlet of the catalytic reforming fixed bed (6) is respectively communicated with a gas phase outlet of the gas-solid separator I (3) through a gas path quick switching valve (10); and a regeneration gas inlet is formed at the bottom of the catalytic reforming fixed bed (6).
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