CN116987533A - Method and device for efficiently preparing hydrogen-rich synthetic gas by biomass gasification on-line upgrading - Google Patents
Method and device for efficiently preparing hydrogen-rich synthetic gas by biomass gasification on-line upgrading Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 82
- 239000002028 Biomass Substances 0.000 title claims abstract description 67
- 238000002309 gasification Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 18
- 239000011707 mineral Substances 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 3
- 239000010453 quartz Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 28
- 235000010755 mineral Nutrition 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 14
- 235000012255 calcium oxide Nutrition 0.000 claims description 14
- 229920000742 Cotton Polymers 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000007792 addition Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C10J3/723—Controlling or regulating the gasification process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/14—Handling of heat and steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
- 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
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
-
- 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
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a method for preparing hydrogen-rich synthetic gas by biomass gasification on-line quality improvement, which comprises the steps of placing a certain amount of calcium-based natural minerals and biomass in a filler bed layer of a gasification reactor according to a ratio of 0.5:1-2:1, simultaneously injecting deionized water into the reactor at a constant speed through an electric control injection pump to form a steam atmosphere with a certain concentration, and carrying out 700-900 DEG C o Under the condition C, rapidly putting the biomass raw material into a reactor for gasification reaction to obtain H 2 A hydrogen-rich synthesis gas product with a controllable CO ratio. Unlike available technology, which introduces steam alone to gasify biomass to prepare synthetic gas, the present invention uses steam and calcium-base natural mineral simultaneously in the biomass gasifying process to upgrade biomass in-situThe primary volatile component formed by thermal depolymerization is absorbed CO by calcium-based natural minerals in a steam atmosphere 2 Promoting the chemical balance of water gas shift reaction in gasification process, activating the C-C and C-H bonds in biomass macromolecules to promote efficient fracture, and promoting H efficiently 2 And the generation improves the conversion efficiency and reduces the loss of energy and raw materials.
Description
Technical Field
The invention relates to a method and a device for preparing hydrogen-rich synthetic gas, in particular to a method and a device for preparing hydrogen-rich synthetic gas efficiently by biomass gasification on-line quality improvement.
Background
Synthesis gas product H produced by traditional biomass gasification process 2 The ratio of the/CO is low, the effective regulation and control are difficult, and the application scene of the biomass synthesis gas preparation technology is limited. Steam is introduced in the gasification process, so that the reactions such as methane steam reforming, water gas reaction, water gas conversion and the like can be promoted, and H is improved 2 The ratio of the gas to the water is increased, and the quality of the synthesis gas is improved. Lin et al demonstrated that increasing steam addition promoted methane reforming reactions, H, using a two-stage fluidized bed gasifier 2 The yield is obviously improved. Martinez et al found that increasing the steam addition also promoted the decomposition of tar byproducts and reduced C in the syngas 3 -C 4 And unsaturated C 2 The compound is beneficial to the subsequent synthetic gas processing procedure. However, most of the reactions in the gasification process are strong endothermic reactions, and the heat in the system is consumed by introducing steam, so that the gasification efficiency of biomass is reduced; while independently introducing steam, H in the synthesis gas obtained by biomass gasification 2 The content is still low, and H 2 The CO ratio is difficult to flexibly adjust, thereby limiting the subsequent industrial application scenarios of the synthesis gas product. At present, an off-line catalytic upgrading method is often adopted to further promote biomass gasificationThe hydrogen content in the obtained synthesis gas is that the primary liquid phase and gas phase products obtained by depolymerizing biomass are collected first, and then noble metals such as platinum, gold, ruthenium and the like are utilized for catalytic reforming, so that the hydrogen-rich synthesis gas product with high added value is obtained. However, the noble metal off-line catalytic upgrading technology is adopted, the noble metal catalyst is expensive and not easy to obtain, and meanwhile, the processes of cooling collection, heating reforming and cooling collection again of the product can cause a great deal of energy consumption and raw material loss. It can be seen that the existing biomass gasification upgrading process with separate steam introduction and off-line catalytic reforming is difficult to obtain the hydrogen-rich synthetic gas product efficiently and at low cost.
Disclosure of Invention
The invention aims to provide a method and a device for preparing hydrogen-rich synthetic gas efficiently by biomass gasification on-line upgrading. The invention applies steam and cheap and easily available calcium-based natural minerals to biomass gasification process simultaneously, improves primary volatile matters formed by heating and depolymerizing biomass on line through the synergistic effect of the steam and the calcium-based natural minerals, promotes the breaking of macromolecular C-C and C-H bonds of the volatile matters, and adsorbs CO in a system 2 Thereby changing the balance of the water gas shift reaction and efficiently improving the yield and H of the synthesis gas 2 The ratio of the biomass resources is improved, and the biomass resources are utilized efficiently and cleanly.
The technical scheme of the invention is as follows: a method for preparing hydrogen-rich synthetic gas by biomass gasification on-line quality improvement comprises the steps of placing a certain amount of calcium-based natural minerals and biomass in a filler bed layer of a gasification reactor according to a ratio of 0.5:1-2:1, simultaneously injecting deionized water into the reactor at a constant speed through an electric control injection pump to form a steam atmosphere with a certain concentration, rapidly putting biomass raw materials into the reactor at 700-900 ℃ for gasification reaction, and obtaining H 2 A hydrogen-rich synthesis gas product with a controllable CO ratio.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement and high efficiency of biomass gasification, the calcium-based natural minerals comprise quicklime and dolomite.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification, the mass ratio of the deionized water to the biomass raw material is 5-20.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement and high efficiency of biomass gasification, the reaction residence time of the primary volatile matters of the biomass is 20min.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement and high efficiency of biomass gasification, the biomass is lignocellulose biomass.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement and high efficiency of biomass gasification, the reaction temperature is 850 ℃.
In the method for preparing the hydrogen-rich synthetic gas by on-line quality improvement and high efficiency of biomass gasification, the injection amount of the deionized water is 5-20 mL/h.
The device for preparing the hydrogen-rich synthetic gas by biomass gasification on-line quality improvement efficiently comprises a quartz tube, wherein a packed bed is arranged in the middle of the inside of the quartz tube, quartz blue is further suspended in the quartz tube above the packed bed, an injection pump is communicated with the top of the quartz tube, a condensing system is communicated with the bottom of the quartz tube through a pipeline, a cotton filtering device is communicated with the condensing system through a pipeline, the tail end of the cotton filtering device is connected with a discharge pipeline, and the quartz tube passes through a vertical tubular furnace.
In the device for preparing the hydrogen-rich synthetic gas by online quality improvement of biomass gasification, the head end of the quartz tube is also connected with a gas flow controller through a pipeline; the cotton filter equipment end is connected with the gas analysis appearance through the flowmeter, and the gas analysis appearance is connected with the computer.
In the device for preparing the hydrogen-rich synthetic gas by biomass gasification on-line quality improvement and high efficiency, the condensing system comprises a plurality of air collection cylinders, the air collection cylinders are sequentially connected through pipelines, 2 pipelines are arranged in each air collection cylinder, an air inlet pipeline and an air outlet pipeline are respectively arranged at the bottom of the air collection cylinder, an air outlet of the air inlet pipeline is arranged at the top of the air collection cylinder, and the air collection cylinder is arranged in a plastic incubator of an ice-water mixture.
The invention has the beneficial effects that: compared with the prior art, the invention is different from the prior process for preparing the synthetic gas by independently introducing steam to gasify biomass, and the invention simultaneously uses steam and calcium-based natural minerals in the biomass gasification process to online upgrade the primary formed by the heated depolymerization of biomassThe CO is adsorbed by the calcium-based natural minerals in a steam atmosphere 2 Promote the chemical balance of water gas shift reaction in gasification process, activate C-C and C-H bonds in biomass macromolecules to promote efficient fracture and promote H 2 And (5) generating. In the reaction system, primary volatile matters formed by heated depolymerization of biomass flow through a mineral bed layer under the pushing of carrier gas, steam reforming is carried out under the catalysis of minerals, the biomass is not in direct contact with calcium-based natural minerals, and inorganic ash contained in the biomass is left in a quartz basket. This solution has three distinct advantages: (1) The adverse effect of ash content of biomass on synthesis gas generation is weakened; (2) The limitation of heat and mass transfer between solid and solid phases caused by direct contact of biomass and calcium-based natural minerals is avoided; (3) The primary volatile component has short transmission distance, and once the volatile component escapes, the catalytic steam reforming is immediately carried out, and side reactions such as volatile component dehydrogenation, addition and the like are restrained, so that the gas selectivity is improved, and the loss of energy and raw materials is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of the device of the present invention;
FIG. 2 is a schematic view showing the effect of comparative example 1;
FIG. 3 is a schematic view showing the effect of comparative example 2;
FIG. 4 is a schematic view showing the effect of comparative example 3;
FIG. 5 is a schematic effect diagram of embodiment 1;
FIG. 6 is a schematic effect diagram of embodiment 2;
FIG. 7 is a schematic view showing the effect of embodiment 3;
fig. 8 is a schematic diagram showing the effect of example 4.
Reference numerals: 1-injection pump, 2-gas flow controller, 3-quartz tube, 4-Dan Yinglan, 5-vertical tube furnace, 6-condensing system, 7-cotton filter, 8-flowmeter, 9-gas analyzer, 10-packed bed.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
The device for preparing the hydrogen-rich synthetic gas by on-line quality improvement through biomass gasification adopted in the following embodiment comprises a gas flow controller 2, a quartz tube 3, a condensing system 6, a cotton filtering device 7 and a gas analyzer 9 which are sequentially connected, wherein the system also comprises a vertical tube furnace 5, and the vertical tube furnace 5 is used for heating the quartz tube 3; the quartz tube 3 is also connected with a syringe pump 1, and the syringe pump 1 is used for adding water into the quartz tube 3; a packing bed layer 10 is arranged in the quartz tube 3; the gas flow controller 2 is used for controlling the flow of nitrogen; the quartz tube 3 is internally suspended Dan Yinglan; the condensing system 6 comprises two empty gas cylinders and a plastic incubator filled with an ice-water mixture, and the empty gas cylinders are cooled by the ice-water mixture; the cotton filter device 7 can realize the filtration and impurity removal of gas; a flowmeter 8 is also arranged between the cotton filtering device 7 and the gas analyzer 9 and is used for monitoring the gas flow.
The method of the present invention is applicable to various biomasses, and the biomasses and calcium-based natural minerals used in the following examples are represented by water yeast Liu Muxie and quicklime.
Embodiments of the invention:
the reaction device for on-line biomass gasification quality improvement is shown in fig. 1, and the specific implementation process of the on-line biomass gasification quality improvement experiment is as follows:
(1) A certain amount of quicklime is subjected to tabletting and sieving (50 meshes) treatment and is placed on a packed bed layer 10 in a quartz tube 3 in advance;
(2) Introducing 400mL/min of high-purity N 2 Removing air in the quartz tube 3 as carrier gas, and heating to a set temperature;
(3) Injecting a certain amount of deionized water (5-20 mL/h) into the quartz tube 3 at uniform speed by utilizing the electronically controlled injection pump 1, and heating the water drops in the falling process to form a steam atmosphere with a certain concentration;
(4) And (3) placing the quartz basket 4 filled with the sawdust biomass raw material into a heating area for 20min, cooling the generated synthesis gas by a condensing system 6 under the pushing of carrier gas, filtering by a cotton filtering device 7, and then entering an online gas analyzer 9 for real-time monitoring of components.
(5) It is proposed that the quartz basket 4 terminate the biomass gasification process.
According to the above procedure, 4 examples were set, each of which had the quicklime and deionized water (steam) additions shown in Table 1, and 3 comparative examples were set, each of which was identical to the treatment group except for whether or not the calcium-based mineral or steam was added.
The above process takes place in the high temperature heating zone as follows:
C x H y O z →H 2 +CO+CO 2 +CH 4 1 (1)
C x H y O z +H 2 O→H 2 +CO 2
C+H 2 O→H 2 +CO 3
CxHy+H 2 O→3H 2 +CO 4
CO+H 2 O→H 2 +CO 2 5. The method is to
CaO+CO 2 →CaCO 3 6. The method is to
Table 1 reaction conditions for each of the examples and comparative examples
Wherein "-" represents no addition.
The gas production characteristics and the like of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2, in which the synthesis gas main component H 2 、CO、CO 2 、CH 4 And C n H m The distribution of hydrocarbons is shown in fig. 2 to 8, wherein fig. 2 is the result of comparative example 1, fig. 3 is the result of comparative example 2, fig. 4 is the result of comparative example 3, fig. 5 is the result of example 1, fig. 6 is the result of example 2, fig. 7 is the result of example 3, and fig. 8 is the result of example 4.
TABLE 2 gas production efficiency and gas production characteristics for each of examples and comparative examples
| Total gas yield (mL/g) | Cold air efficiency CGE (%) | H 2 Ratio of CO | |
| Example 1 | 944.67 | 63.08 | 0.63 |
| Example 2 | 1133.33 | 71.63 | 0.96 |
| Example 3 | 1358.13 | 87.30 | 0.82 |
| Example 4 | 1254.31 | 81.41 | 0.87 |
| Comparative example 1 | 1149.82 | 80.29 | 0.37 |
| Comparative example 2 | 778.11 | 53.69 | 0.35 |
| Comparative example 3 | 853.39 | 65.02 | 0.14 |
It can be seen that the biomass gasification gas production characteristics are different for different deionized water pumping rates compared to the anhydrous condition of comparative example 1. H when the deionized water pumping rate was transitioned from comparative example 1 to examples 1 and 2 2 And CO 2 Greatly facilitates the release of the catalyst from 243.93mL/g to 399.90mL/g and from 139.29mL/g to 220.58mL/g, respectively, the CO is greatly reduced from 655.35mL/g to 418.01mL/g, and the CH is greatly reduced 4 The yield of (c) is almost unchanged. For H 2 The ratio of/CO was up to 0.96 at a deionized water pumping rate of 15mL/h, approximately 3 times that of anhydrous (0.37). Thus, a deionized water pumping rate of 15mL/h is the optimal condition for steam introduction, which produces a relatively high quality synthesis gas.
In contrast to the catalyst-free steam gasification experiment of comparative example 2, the addition of quicklime effectively increased H compared to steam gasification without quicklime 2 Yield is improved to 2 the/CO ratio, producing a more valuable synthesis gas. This is due to CO 2 Is captured in CaO solid phase to generate carbonation reaction to form CaCO 3 ，H 2 The concentration increases significantly. As can be seen from the results, when the addition amount of quicklime is 15g, H 2 the/CO ratio reached a higher level of 95.67%. These results indicate that the steam gasification-related reactions (formulas 1 to 6) can be effectively promoted by increasing the addition amount of quicklime, and the yield and quality of the synthesis gas can be improved.
In combination, the independent addition of steam only improves the synthesis gas H of the traditional gasification process 2 The ratio of the air to the CO is slightly reduced, and the total gas yield and the cold air efficiency are slightly reduced; while the addition of quicklime alone results in total gas yield, cold air efficiency and H 2 /CThe O proportion is improved by a small margin, but H 2 The yield is still lower<250mL/g material). When CaO and steam are used together, the total gas yield, the cold air efficiency and H can be simultaneously improved 2 Three indexes of the ratio of the catalyst to CO can respectively reach 1358.13mL/g of material, 87.30 percent and 0.96, wherein the highest is that of the synthetic gas H 2 The yield can reach 458.57mL/g Material Is approximately 2 times of the hydrogen production amount of the lime added alone. On the other hand, it can be seen from the lateral comparison between the examples that H can be realized by controlling the addition amounts of quicklime and steam 2 The flexible regulation of the ratio of the/CO is operated in actual production, and high-quality synthesis gas can be efficiently obtained by only adding a simple electric control injection pump device and a calcium-based natural mineral filler bed. The calcium-based natural minerals and steam in the technology are cheap and easy to obtain, and the production cost is not obviously increased.
Claims (10)
1. The method for preparing the hydrogen-rich synthetic gas by biomass gasification on-line upgrading is characterized by comprising the following steps of: placing a certain amount of calcium-based natural minerals and biomass in a filler bed layer of a gasification reactor according to a ratio of 0.5:1-2:1, simultaneously injecting deionized water into the reactor at a constant speed through an electric control injection pump to form a steam atmosphere with a certain concentration, and performing constant speed injection on the deionized water in a range of 700-900 o Under the condition C, rapidly putting the biomass raw material into a reactor for gasification reaction to obtain H 2 A hydrogen-rich synthesis gas product with a controllable CO ratio.
2. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the calcium-based natural minerals include quicklime and dolomite.
3. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the mass ratio of the deionized water to the biomass raw material is 5-20.
4. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the reaction residence time of the primary volatile of biomass was 20min.
5. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the biomass is a lignocellulosic biomass.
6. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the reaction temperature was 850 o C。
7. The method for efficiently preparing hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification according to claim 1, which is characterized in that: the injection amount of the deionized water is 5-20 mL/h.
8. The device for preparing the hydrogen-rich synthetic gas by on-line quality improvement of biomass gasification is characterized in that: the novel high-temperature-resistant quartz tube furnace comprises a quartz tube (3), wherein a packed bed (10) is arranged in the middle of the inside of the quartz tube (3), quartz blue (4) is further suspended in the quartz tube (3) above the packed bed (10), an injection pump (1) is communicated with the top of the quartz tube (3), a condensing system (6) is communicated with the bottom of the quartz tube (3) through a pipeline, a cotton filtering device (7) is communicated with the condensing system (6) through the pipeline, the tail end of the cotton filtering device (7) is connected with a discharge pipeline, and the quartz tube (3) penetrates through a vertical tube furnace (5).
9. The device for on-line upgrading and efficient preparation of hydrogen-rich synthetic gas by biomass gasification according to claim 8, wherein the device is characterized in that: the head end of the quartz tube (3) is also connected with a gas flow controller (2) through a pipeline; the tail end of the cotton filtering device (7) is connected with a gas analyzer (9) through a flowmeter (8), and the gas analyzer (9) is connected with a computer.
10. The device for on-line upgrading and efficient preparation of hydrogen-rich synthetic gas by biomass gasification according to claim 8, wherein the device is characterized in that: the condensing system (6) comprises a plurality of air cylinders, the air cylinders are sequentially connected through pipelines, 2 pipelines are arranged in each air cylinder, an air inlet pipeline and an air outlet pipeline are respectively arranged, an air inlet of the air inlet pipeline is positioned at the bottom of the air cylinder, an air outlet of the air outlet pipeline is positioned at the top of the air cylinder, and the air cylinders are arranged in a plastic heat-insulating box of an ice-water mixture.
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| CN113600172A (en) * | 2021-08-23 | 2021-11-05 | 南京工业大学 | Alkaline catalyst and preparation method and application thereof |
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| CN104178225A (en) * | 2014-08-07 | 2014-12-03 | 华中师范大学 | Device and method for preparing hydrogen-enriched gas through in-situ catalytic gasification of biomasses |
| CN110155948A (en) * | 2019-04-11 | 2019-08-23 | 江苏大学 | A kind of biomass graded gasification hydrogen-producing method |
| CN113600172A (en) * | 2021-08-23 | 2021-11-05 | 南京工业大学 | Alkaline catalyst and preparation method and application thereof |
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