CN114618388A - Device and process for preparing ammonia by using biomass - Google Patents
Device and process for preparing ammonia by using biomass Download PDFInfo
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- CN114618388A CN114618388A CN202210260367.1A CN202210260367A CN114618388A CN 114618388 A CN114618388 A CN 114618388A CN 202210260367 A CN202210260367 A CN 202210260367A CN 114618388 A CN114618388 A CN 114618388A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 55
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 112
- 238000000197 pyrolysis Methods 0.000 claims abstract description 99
- 239000000571 coke Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003546 flue gas Substances 0.000 claims abstract description 16
- 238000002309 gasification Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000002485 combustion reaction Methods 0.000 claims description 25
- 238000004891 communication Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000006479 redox reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000003570 air Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
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- 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
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention relates to the technical field of ammonia production, in particular to a device and a process for producing ammonia by using biomass, wherein the device comprises a pyrolysis reactor connected with a solar heat collector; the gas-solid separator is communicated with the pyrolysis reactor; the chemical chain gasification unit comprises a gasifier and an air reactor, wherein the gasifier is communicated with the gas-solid separator and communicated with the air reactor through a circulating pipeline; the gas holder is communicated with the gasifier; the ammonia production unit comprises a carbothermic reactor and a steam reactor which are communicated, and the carbothermic reactor is respectively communicated with the air reactor, the gas-solid separator, the gas holder and the pyrolysis reactor; and the combustor is respectively communicated with the gas holder and the pyrolysis reactor. When the device is used for producing ammonia, the solar energy and the combustible gas are combusted to provide heat required by pyrolysis in the daytime, and partial coke is adopted to be combusted to release heat at night and the combustible gas is combusted to generate hot flue gas to be conveyed to the pyrolysis reactor to provide heat required by pyrolysis heat supply.
Description
Technical Field
The invention relates to the technical field of ammonia production, in particular to a device and a process for producing ammonia by using biomass.
Background
With the increasing exhaustion of fossil energy and the environmental problems caused by the use of fossil energy, various alternative energy sources have come to the fore, and biomass is the energy source which is second to coal, petroleum and natural gas and is the fourth of the total energy consumption of the world, and plays an important role in the whole energy system. The biomass energy has the characteristics of environmental friendliness, low carbon, cleanness, reproducibility and the like, has the advantages of wide distribution and stable supply, and the development of the biomass energy is a necessary requirement for comprehensively realizing the vogue of villages and is an important measure for realizing the emission reduction promise of China.
The ammonia can be liquefied under the pressure of 2.0-2.5 MPa, a refrigeration heat-preservation system is not needed, and the ammonia storage material has the advantages of high energy density, safety and the like, is an excellent hydrogen storage material, and can solve the problem of poor safety in hydrogen storage and transportation.
The raw materials of the existing ammonia synthesis technology are coal and natural gas as main materials, hydrogen is firstly prepared from the raw materials, and the hydrogen and the nitrogen generate ammonia under the action of a catalyst. However, the existing ammonia synthesis technology needs to consume fossil fuel, the reaction preparation process needs higher temperature and pressure, and hydrogen generated in the reaction process is not easy to store and can only be produced quantitatively.
Disclosure of Invention
In view of the above technical problems, the present invention provides the following technical solutions:
the invention provides a device for producing ammonia by using biomass, which comprises:
the pyrolysis reactor is connected with a solar heat collector;
a gas-solid separator in communication with the pyrolysis reactor;
the chemical chain gasification unit comprises a gasifier and an air reactor, the gasifier is communicated with the gas-solid separator, and the gasifier is communicated with the air reactor through a circulating pipeline;
the gas holder is communicated with the gasifier;
the ammonia production unit comprises a carbothermic reactor and a steam reactor, the carbothermic reactor is communicated with the steam reactor through a circulating pipeline, and the carbothermic reactor is respectively communicated with the air reactor, the gas-solid separator, the gas holder and the pyrolysis reactor; and
and the combustor is respectively communicated with the gas holder and the pyrolysis reactor.
Preferably, the carbothermic reactor is connected with the gas-solid separator and the pyrolysis reactor through a three-way pipeline, and a control valve is arranged at a port of the three-way pipeline, which is close to the pyrolysis reactor.
Preferably, the gas holder is connected with the burner and the carbothermic reactor through communicating pipes respectively, and a valve is arranged on the communicating pipe between the gas holder and the burner.
Preferably, the burner is replaced with a chemical looping combustion device, and the chemical looping combustion device is in communication with the carbothermic reactor.
Preferably, the device also comprises a dryer which is connected with the pyrolysis reactor through a material conveying pipeline and a flue gas pipeline respectively.
Preferably, the gasifier further comprises a heat exchange unit, wherein the heat exchange unit consists of a first heat exchanger, a second heat exchanger and a third heat exchanger, the first heat exchanger is connected between the gasifier and the gas holder, and the first heat exchanger is connected with the air reactor; the second heat exchanger is connected between the carbothermic reactor and the steam reactor, and the second heat exchanger is respectively connected with the burner and the pyrolysis reactor; and the third heat exchanger is connected to the steam reactor.
The invention also provides a process for preparing ammonia gas by using the device for preparing ammonia from biomass, which comprises the following steps:
s1, supplying the biomass subjected to moisture removal into the pyrolysis reactor for pyrolysis reaction, and separating pyrolysis products through the gas-solid separator to obtain coke, tar and combustible gas;
wherein the heat for pyrolysis in the pyrolysis reactor is supplied by heat exchange of the solar heat collector and combustion of the combustor; or
Heat supply from partial coke resupply to combustion in the pyrolysis reactor and the burner combustion heat supply; or
Heat supply from combustion of said burner;
s2, adding a high-valence metal oxide into the air reactor for oxidation-reduction reaction, conveying the obtained low-valence metal oxide, tar and combustible gas in S1 into the gasifier for oxidation-reduction reaction to obtain the high-valence metal oxide and gas, storing the gas into the gas holder, and allowing the high-valence metal oxide to enter the air reactor for continuous oxidation-reduction reaction;
s3, adding AlN and water into the steam reactor, and reacting to obtain a product Al2O3And NH3，Al2O3With N produced in the air reactor2And S1, conveying part or all of the coke in the S1 to the carbothermic reactor to carry out carbothermic reaction to obtain AlN and CO, continuously conveying the AlN to the steam reactor to participate in the reaction, and conveying the CO to the gas holder to be stored so as to be used for regulating the pressure or conveying the CO to the combustor.
Preferably, in S1 the first step of the method,
the step of removing water is to reduce the water content in the biomass to be less than 5 percent at the temperature of 150-250 ℃;
the temperature of the pyrolysis reaction is 400-900 ℃.
Preferably, in S2, the reaction temperature in the gasifier and the air reactor is 1000 ℃ to 1200 ℃.
Preferably, in S3, the reaction temperature in the carbothermic reactor is 900 to 1500 ℃ and the reaction temperature in the steam reactor is 800 to 1500 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. when the device for preparing ammonia by using biomass is used for preparing ammonia gas, the coke for combustion reaction of the pyrolysis reactor, the storage amount of CO in the gas holder and the intermittent input amount of heat exchange of the solar heat collector are controlled, so that the whole preparation process flow has strong schedulability, can continuously run for 24 hours, and can be suitable for preparing ammonia by using different biomass raw materials.
2. When the device for preparing ammonia by using biomass provided by the invention is used for preparing ammonia gas, the heat supply modes in the day and at night are different in the pyrolysis process, heat is provided for pyrolysis by using a solar heat collector for heat exchange and combustible gas for combustion in a combustor in the day, and heat is provided for pyrolysis by using partial coke for heat release and combustible gas for combustion in the combustor at night to generate hot smoke and is conveyed to a pyrolysis reactor for providing heat for pyrolysis. Because the whole pyrolysis process has different heat supply modes in the day and at night, the adjustability is high in the actual utilization process.
3. According to the biomass ammonia production device provided by the invention, in the ammonia production process, the flue gas passes through the heat exchanger, the pyrolysis reactor and the dryer in sequence, so that the temperature requirements of all devices are met, the gradient utilization of the heat of the flue gas is realized, and the energy utilization efficiency is high.
4. The ammonia preparation process provided by the invention is carried out by a carbothermic method, the raw materials are easy to obtain, and the generated gas is easy to store and can be recycled to the pyrolysis reaction; meanwhile, the method can realize mass production of ammonia.
Drawings
FIG. 1 is a schematic connection diagram of a biomass ammonia plant provided by an embodiment of the invention;
FIG. 2 is a diagram of the heat distribution for the pyrolysis ammonia production by the biomass ammonia production device provided by the invention;
FIG. 3 is a schematic structural view of a double fluidized bed;
FIG. 4 is another schematic illustration of the dual fluidized bed configuration.
Description of reference numerals: 1. the system comprises a dryer, 2, a pyrolysis reactor, 3, a solar heat collector, 4, a gas-solid separator, 5, a chemical chain gasification unit, 6, a gasifier, 7, an air reactor, 8, a first heat exchanger, 9, a gas holder, 10, a valve, 11, a burner, 12, an ammonia production unit, 13, a carbothermic reactor, 14, a second heat exchanger, 15, a steam reactor, 16, a third heat exchanger, 17 and a control valve.
Detailed Description
The present invention is further described below by way of examples, but the present invention is not limited by these examples. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
A device for preparing ammonia by using biomass is disclosed, and shown in figure 1, the device comprises a pyrolysis reactor 2, a gas-solid separator 4, a chemical chain gasification unit 5, a gas holder 9, an ammonia preparation unit 12 and a combustor 11, wherein the pyrolysis reactor 2 is connected with a solar heat collector 3, the gas-solid separator 4 is communicated with the pyrolysis reactor 2, the chemical chain gasification unit 5 comprises a gasifier 6 and an air reactor 7, the gasifier 6 is communicated with the gas-solid separator 4, and the gasifier 6 is communicated with the air reactor 7 through a circulating pipeline; the gas holder 9 is communicated with the gasifier 6; the ammonia production unit 12 comprises a carbothermic reactor 13 and a steam reactor 15, the carbothermic reactor 13 is communicated with the steam reactor 15 through a circulating pipeline, and the carbothermic reactor 13 is respectively communicated with the air reactor 7, the gas-solid separator 4, the pyrolysis reactor 2 and the gas holder 9; the burner 11 is respectively communicated with the gas holder 9 and the pyrolysis reactor 2.
It should be noted that the ammonia production unit 12 may be replaced by a dual fluidized bed of the prior art, the dual fluidized bed having the structure shown in fig. 3-4. The steam reactor 15 may be replaced by a steam autoclave of the prior art.
The device for producing ammonia by biomass takes different times in the day and at night into consideration during design, namely, the heat supply condition of the system under the condition of solar heat supply is available, and efficient ammonia production can be realized. In particular, when in use:
the dried biomass enters the pyrolysis reactor 2, and air heating is insulated in the pyrolysis reactor 2. The products of biomass pyrolysis are coke, tar and combustible gas, wherein the tar is gaseous at high temperature and is mixed with the combustible gas. The coke and gas generated by pyrolysis are subjected to gas-solid separation in a gas-solid separator 4;
tar and combustible gas generated by biomass pyrolysis enter a chemical chain gasification unit 5 for gasification reaction to generate CO and CO2A predominantly gaseous species;
in the daytime, coke produced by biomass pyrolysis is all used for the carbothermic reaction; at night, a part of coke generated by biomass pyrolysis enters the pyrolysis reactor 2 to burn and release heat to provide energy for biomass pyrolysis, and the rest enters the carbothermic reactor 13 to react with the oxygen carrier and H2O and N2(produced by reaction of chemical looping gasification unit 5) to form NH3And CO. NH (NH)3After cooling, the CO is collected and stored in the gas holder 9, and is combusted to release heat according to the heat demand of the system. The ash content left after the coke reaction is carried into the gas holder 9 by CO, the gas flow rate in the gas holder 9 is reduced, and the ash content is settled at the bottom of the gas holder by gravity and is removed periodically.
Go to oneThe burner 11 can be replaced by a chemical-looping combustion device (Tianjin allows the same technologies and technologies Co., Ltd.) in the chemical-looping combustion technology, and the air combustion of the burner 11 is replaced by the chemical-looping combustion to generate N2May be fed to the carbothermic reactor 13 to be involved in the ammonia production reaction or may be directly vented.
Further, the carbothermic reactor 13 is connected with the gas-solid separator 4 and the pyrolysis reactor 2 through a three-way pipeline, and a control valve 17 is arranged at a port of the three-way pipeline close to the pyrolysis reactor 2.
Further, the gas holder 9 is connected with the burner 11 and the carbothermic reactor 13 through communication pipes, and a valve 10 is arranged on the communication pipe between the gas holder 9 and the burner 11. The valve 10 is used to regulate the amount of combustible gas in the gas holder 9 entering the burner 11.
Further, still include desicator 1, desicator 1 and pyrolysis reactor 2 are connected through conveying pipeline and flue gas pipeline respectively. The biomass first enters a dryer 1 and is dried in the dryer 1 to remove moisture. The heat source in the dryer 1 is derived from the heat generated by the combustion of combustible gas in the burner 11, and the heat enters the pyrolysis reactor 2 to supply heat for the pyrolysis reaction, and then is conveyed into the dryer 1 through a flue gas pipeline.
Further, the system also comprises a heat exchange unit, the heat exchange unit can cool or heat materials entering different reactors to the optimal temperature, the heat exchange unit comprises a first heat exchanger 8, a second heat exchanger 14 and a third heat exchanger 16, the first heat exchanger 8 is connected between the gasifier 6 and the gas holder 9, and the first heat exchanger 8 is communicated with the air reactor 7; the second heat exchanger 14 is connected between the carbothermic reactor 13 and the steam reactor 15, and the second heat exchanger 14 is respectively communicated with the burner 11 and the pyrolysis reactor 2; the third heat exchanger 16 is communicated with the steam reactor 15.
Example 2
A process for producing ammonia using the apparatus provided in example 1, comprising:
s1, the biomass from the dryer 1 enters the pyrolysis reactor 2, pyrolysis is carried out in the pyrolysis reactor 2, the pyrolysis temperature is controlled to be 400-900 ℃, the pyrolysis time is 0.5-1 second, and the products are coke, tar and combustible gas. The pyrolysis process is regulated according to the method of the existence of solar energy. The method comprises the following specific steps:
in the daytime, solar energy from the solar heat collector 3 enters the pyrolysis reactor 2 through heat exchange to supply heat for pyrolysis reaction, and at the moment, high-temperature flue gas from the combustor 11 is cooled by the second heat exchanger 14 and then is conveyed to the pyrolysis reactor 2 to supply heat required by the pyrolysis reaction;
at night, more combustible gas is needed to enter the burner 11 for combustion and heat release because of the absence of solar energy. CO gas is produced from the carbothermic reactor 13 into the gas cabinet 9 and the valve 10 is adjusted to allow more CO gas to enter the burner 11. The gas in the gas holder 9 is pressure-regulated, and part of the gas enters the combustor 11 to be combusted according to the heat requirement after the pressure is met. The gas in the gas holder 9 is mainly CO2、CO、H2、H2And O. The whole process adopts a mode of heating and pyrolyzing the flue gas, namely the flue gas exchanges heat in the pyrolysis reactor 2. In the operation of the system, the process is carried out according to the above process, all the gas in the gas holder 9 is used for burning to generate hot flue gas, and the whole system can also achieve normal operation. However, the chemical-looping gasification unit 5 and the ammonia production unit 12 are not in the optimal temperature state, and the ammonia production effect is poor. Meanwhile, no gas is stored in the gas tank 9, so that the system cannot regulate the pressure, and is stable and poor in safety performance. Therefore, under the condition of no solar energy supply at night, part of coke is separated from the gas-solid separator 4, and is sent into the pyrolysis reactor 2 through the control valve 17 and air to be combusted and supplied with heat, and part of combustible gas in the gas holder 9 enters the combustor 11 to be combusted and generated into hot flue gas to be supplemented, or the combustible gas in the gas holder 9 directly enters the combustor 11 to be combusted and supplied with heat, and the stable operation at night is achieved by adopting the scheme;
s2, the pyrolysis product from the pyrolysis reactor 2 is separated into pyrolysis gas and solid coke by the gas-solid separator 4, and the pyrolysis gas enters the chemical looping gasification unit 5. The pyrolysis gas is mainly tar and combustible gas. Fe from the air reactor 72O3The pyrolysis gas enters a gasifier 6, the temperature of the reactor is 1000-1200 ℃ (tar exists in a gas form in the gasification process), and the product is Fe3O4And CO2CO, and also a small amount of CH4、H2And H2And O, cooling the gas by the first heat exchanger 8 and storing the gas in a gas holder 9. The reaction is predominantly endothermic and heat is provided by the air reactor 7. Fe from gasifier 63O4Enters an air reactor 7 together with air preheated by a first heat exchanger 8 at the temperature of 1000-1200 ℃, and the product is Fe2O3. The reaction is exothermic. Oxygen carrier (Fe) during the whole cycle2O3、Fe3O4) The redox reaction alternately occurs, the time of a single cycle period is 20-50 minutes, and the chemical reaction is as follows:
3Fe2O3+CO→2Fe3O4+CO2，Fe2O3+ Tar → Fe3O4+CO+(H2+CH4+H2O)Small amount of
2Fe3O4+1/2O2→3Fe2O3
S3, sending the solid coke to the ammonia production unit 12, and preheating Al from the steam reactor 15 by the second heat exchanger 142O3And N produced by the air reactor 72Enters a carbothermic reactor 13 (the carbothermic reactor 13 is used for preparing AlN), the temperature of the reactor is 900-1500 ℃, and the products are AlN and CO. Remaining N of the reaction2And storing or emptying after heat exchange and cooling. The reaction is predominantly endothermic and heat is provided by the burner 11 burning gases for heat release. AlN from the carbothermic reactor 13 and H preheated by the heat exchanger 162O enters a steam reactor 15, the temperature is 800-1500 ℃, and the product is Al2O3And NH3。NH3Cooled by the third heat exchanger 16 and collected. The time of a single cycle period is 20-50 minutes. The main reactions occurring in the whole process are:
Al2O3+N2+3C→2AlN+3CO
2AlN+3H2O→Al2O3+2NH3
preparation of NH by the reaction3While generating combustible gas COCO is stored in the gas holder 9 for pressure regulation and is used as a raw material for the combustion reaction of the combustor 11;
wherein, the combustible gas from the chemical chain gasification unit 5 is cooled by a first heat exchanger 8 and then enters a gas holder 9, and the CO from the ammonia production unit 12 enters the gas holder 9 for storage and pressure regulation according to the subsequent heat requirement. The gas in the gas holder 9 is regulated to make the system operate stably, and part of the gas is also fed into the burner 11 according to the subsequent heat requirement. The combustible gas and air from the device are burnt in the burner 11, and high-temperature flue gas is discharged, and the temperature is about 1200 ℃.
The ammonia production unit 12 in the above S3 can be directly replaced by a double fluidized bed in the prior art, and the specific structure and the material reaction flow are shown in fig. 3-4.
Combustible gas CO generated in the process is stored through the gas holder 9, a certain buffering effect is achieved on the whole system, and meanwhile heat required by the operation of the system can be provided by burning CO stored in the daytime at night.
The generated flue gas is subjected to distributed heat exchange through the second heat exchanger 14, the pyrolysis reactor 2 and the dryer 1 in sequence, the principle of 'temperature alignment and cascade utilization' is met, and finally the temperature of the flue gas is maintained at about 150 ℃.
The raw materials used in the whole process are biomass, air and water, and ammonia gas is generated through carbothermic reduction reaction, so that zero carbon emission is achieved.
The heat distribution during the manufacturing process is further described below with reference to fig. 2.
Under the condition that solar energy supplies heat to the pyrolysis furnace in the daytime, biomass firstly enters the dryer 1 for drying, the moisture content is reduced to be below 5%, and then the biomass enters the pyrolysis reactor 2 for pyrolysis to generate coke, tar and combustible gas. Gas-solid separation is carried out on the generated product, the gas is subjected to chemical chain gasification, wherein tar is in a gas state at high temperature, and the gas generated by the chemical chain gasification is CO2、CO、H2、H2O is the main component. A part of the solid coke is used as a raw material to be combusted with air in the pyrolysis reactor 2 to provide heat, the other part of the coke is used as a reducing agent in the carbothermic reactor 13, and combustible gas generated by the ammonia production unit 12 is mainly CO.The gas generated by chemical looping gasification enters the gas holder 9 for storage, and the CO generated by the ammonia production unit 12 also enters the gas holder 9 for pressure regulation and enters the combustor 11 for combustion. The pressure is regulated through the gas holder 9, and the gas is combusted in the combustor 11 as required after meeting the pressure. The high temperature flue gas produced by combustion is used for preheating the reaction raw materials, heating the pyrolysis reactor 2 and drying the biomass.
Taking 10kg/h of corn straw as an example, under the condition that solar energy exists in the daytime, the heat provided by the solar energy is 1000W, all the coke generated by the pyrolysis reactor 2 is used for the reaction of preparing ammonia through thermal conversion, and a part of gas is stored in the gas holder 9. NH produced by the system34.11kg/h, 4.39kg/h coke for ammonia production, 15.52kg/h combustible gas in the gas holder 9 fed into the burner 11, 1.05kg/h combustible gas stored, NH during the reaction3The ratio of/C was 93.6%. At night, in the absence of solar energy, the coke fraction produced by the pyrolysis reactor 2 is used for the thermal conversion ammonia production reaction, and the gas produced is stored in the gas holder 9. NH produced by the system33.29kg/h, 0.88kg/h coke for supplying heat to the pyrolysis reactor 2, 3.52kg/h coke for reacting to produce ammonia, 8.31kg/h combustible gas fed into the combustor 11 in the gas holder 9, 0.93kg/h combustible gas stored, NH in the reaction process3The ratio of/C was 93.47%.
For other biomasses such as wood chips, rice chaff and the like, the corresponding pyrolysis temperature is calculated based on industrial analysis, elemental analysis, calorific value, pyrolysis required heat and the like, and then the ammonia production process is realized through the process flow. It should be noted that the pyrolysis temperature, the amount of coke used for combustion heat supply, the amount of solar energy input, and the amount of CO stored during pyrolysis are relevant.
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (10)
1. An apparatus for producing ammonia from biomass, comprising:
the pyrolysis reactor (2) is connected with a solar heat collector (3);
a gas-solid separator (4) in communication with the pyrolysis reactor (2);
the chemical chain gasification unit (5) comprises a gasifier (6) and an air reactor (7), wherein the gasifier (6) is communicated with the gas-solid separator (4), and the gasifier (6) is communicated with the air reactor (7) through a circulating pipeline;
the gas holder (9) is communicated with the gasifier (6);
an ammonia production unit (12) comprising a carbothermic reactor (13) and a steam reactor (15), wherein the carbothermic reactor (13) is communicated with the steam reactor (15) through a circulating pipeline, and the carbothermic reactor (13) is respectively communicated with the air reactor (7), the gas-solid separator (4), the gas holder (9) and the pyrolysis reactor (2); and
and the combustor (11) is respectively communicated with the gas holder (9) and the pyrolysis reactor (2).
2. The device for producing ammonia by using biomass according to claim 1, wherein the carbothermic reactor (13) is connected with the gas-solid separator (4) and the pyrolysis reactor (2) through a three-way pipeline, and a control valve (17) is arranged at a port of the three-way pipeline, which is close to the pyrolysis reactor (2).
3. The device for producing ammonia from biomass according to claim 2, wherein the gas holder (9) is connected to the burner (11) and the carbothermic reactor (13) through communication pipes, and a valve (10) is disposed on the communication pipe between the gas holder (9) and the burner (11).
4. The apparatus for producing ammonia from biomass according to claim 1, wherein the burner (11) is replaced by a chemical looping combustion apparatus, and the chemical looping combustion apparatus is in communication with the carbothermic reactor (13).
5. The device for producing ammonia from biomass according to claim 1, further comprising a dryer (1), wherein the dryer (1) and the pyrolysis reactor (2) are respectively connected through a material conveying pipeline and a flue gas pipeline.
6. The device for producing ammonia by using biomass according to claim 5, further comprising a heat exchange unit, wherein the heat exchange unit comprises:
the first heat exchanger (8) is connected between the gasifier (6) and the gas holder (9), and the first heat exchanger (8) is communicated with the air reactor (7);
a second heat exchanger (14) connected between the carbothermic reactor (13) and the steam reactor (15), wherein the second heat exchanger (14) is respectively communicated with the burner (11) and the pyrolysis reactor (2); and
and the heat exchanger III (16) is communicated with the steam reactor (15).
7. A process for preparing ammonia gas by using the biomass ammonia production device of any one of claims 1 to 3, which is characterized by comprising the following steps:
s1, supplying the biomass subjected to moisture removal into the pyrolysis reactor (2) for pyrolysis reaction, and separating pyrolysis products through the gas-solid separator (4) to obtain coke, tar and combustible gas;
wherein the heat for pyrolysis in the pyrolysis reactor (2) is generated by heat exchange of the solar heat collector (3) and combustion heat supply of the combustor (11); or
Heat supply from the re-supply of a portion of coke to the combustion in the pyrolysis reactor (2) and heat supply from the combustion in the burner (11); or
-combustion heat supply originating from said burner (11);
s2, adding a high-valence metal oxide into the air reactor (7) to perform an oxidation-reduction reaction, conveying the obtained low-valence metal oxide, tar and combustible gas in the S1 into the gasifier (6) to perform an oxidation-reduction reaction to obtain the high-valence metal oxide and gas, storing the gas into the gas holder (9), and continuously conveying the high-valence metal oxide into the air reactor (7) to perform the oxidation-reduction reaction;
s3, adding AlN and water into the steam reactor (15) to react to obtain a product Al2O3And NH3，Al2O3With N produced in the air reactor (7)2And delivering part or all of the coke in the S1 to the carbothermic reactor (13) for carbothermic reaction to obtain products AlN and CO, wherein AlN continues to enter the steam reactor (15) for reaction, and CO is delivered to the gas holder (9) for storage so as to adjust the pressure or deliver the CO to the combustor (11).
8. The process of claim 7, wherein, in S1,
the step of removing water is to reduce the water content in the biomass to below 5 percent at the temperature of 150-250 ℃;
the temperature of the pyrolysis reaction is 400-900 ℃.
9. The process according to claim 8, wherein the reaction temperature in the gasifier (6) and the air reactor (7) in S2 are both 1000 ℃ to 1200 ℃.
10. The process according to claim 9, characterized in that in S3, the reaction temperature in the carbothermic reactor (13) is 900 ℃ to 1500 ℃ and the reaction temperature in the steam reactor (15) is 800 ℃ to 1500 ℃.
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