CN106675600B - Coal gasification hydrogen production method - Google Patents
Coal gasification hydrogen production method Download PDFInfo
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- CN106675600B CN106675600B CN201510754153.XA CN201510754153A CN106675600B CN 106675600 B CN106675600 B CN 106675600B CN 201510754153 A CN201510754153 A CN 201510754153A CN 106675600 B CN106675600 B CN 106675600B
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- 238000002309 gasification Methods 0.000 title claims abstract description 262
- 239000003245 coal Substances 0.000 title claims abstract description 102
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000002485 combustion reaction Methods 0.000 claims abstract description 91
- 239000007789 gas Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000002093 peripheral effect Effects 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 54
- 238000003786 synthesis reaction Methods 0.000 claims description 54
- 239000002893 slag Substances 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
-
- 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
- C10J2300/093—Coal
-
- 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
- C10J2300/12—Heating the gasifier
- C10J2300/1223—Heating the gasifier by burners
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Industrial Gases (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a method for producing hydrogen by coal gasification, which utilizes a coal gasification device comprising an upper-stage gasification chamber (2) and a lower-stage combustion gasification chamber (1), wherein the peripheral wall of the upper-stage gasification chamber is provided with a plurality of upper nozzles (8b), the peripheral wall of the lower-stage combustion gasification chamber is provided with a plurality of lower nozzles (8a), and at least one of the plurality of upper nozzles is a steam nozzle, and the method comprises the following steps: after the lower-section combustion gasification chamber is preheated, coal fuel and a gasifying agent are introduced into the lower-section combustion gasification chamber through a lower nozzle to generate combustion and gasification reaction, and water vapor is introduced into the upper-section gasification chamber through an upper nozzle to generate water-gas shift reaction, wherein the lower-section combustion gasification chamber is a combustion chamber of coal, and the upper-section gasification chamber does not need coal to participate. In the coal gasification device and the coal gasification method thereof, the water gas shift reaction can be strengthened, the hydrogen yield is increased, and the hydrogen content in the produced synthetic gas is obviously higher than that of the current mainstream entrained flow gasifier.
Description
Technical Field
The invention relates to the field of coal chemical industry, in particular to a coal gasification hydrogen production method which can produce synthesis gas with higher hydrogen content.
Background
The coal hydrogen production technology mainly takes coal gasification hydrogen production as a main technology. The coal gasification hydrogen production is that coal is gasified to obtain carbon monoxide, hydrogen, water and carbon dioxideThe synthesis gas of the main component is purified, converted and separated by carbon monoxide (CO), purified and the like to obtain the product hydrogen with certain purity. The technological process of coal gasification hydrogen production technology generally comprises coal gasification, coal gas purification, CO conversion and H2Purification and other main production links.
The coal gasification device is key equipment for producing hydrogen by coal gasification. The carbon-containing fuel (i.e. coal fuel, such as dry coal powder or coal water slurry) is combusted and gasified in the coal gasification device to obtain the synthesis gas with carbon monoxide, hydrogen, water and carbon dioxide as main components. In the prior art, a coal gasification apparatus generally has a single combustion gasification chamber, coal fuel, a gasification agent (such as oxygen), and the like are combusted and gasified in the combustion gasification chamber, and the obtained synthesis gas flows out of the coal gasification apparatus and enters a next-stage process device. However, the hydrogen content of the synthesis gas produced by coal gasification plants of the prior art is generally not high, such as H in the synthesis gas produced by dry coal powder gasification2The content is usually not higher than 30%.
Some studies have been made in the prior art, for example, in us patent document us 2005/0039400 a1, a hydrogen production apparatus is disclosed in which a hydrogen selective permeable membrane is provided in a fluidized bed gasification furnace, and a synthesis gas flowing out of the gasification furnace is filtered by the hydrogen selective permeable membrane to obtain a product gas with a higher hydrogen content. But the disadvantages are that the gasification intensity of the fluidized bed gasification furnace is low, the load is low, the separation membrane in the furnace is easy to be polluted and blocked by fly ash, and H is treated under the conditions of high temperature and high pressure in the gasification furnace2The requirement of the separation membrane material is high, and the use condition of the separation membrane is harsh.
In addition, chinese patent document CN 202430187U discloses a three-stage fluidized bed hydrogen production apparatus, which is divided into three processes of coupled coal gasification, carbon dioxide capture by calcium-based adsorbent and calcium carbonate calcination, and the carbon dioxide is captured by the calcium-based adsorbent to increase the hydrogen content. The coal briquette gasification hydrogen production device has the disadvantages of complex reactor structure, low fluidized bed gasification reaction strength, large calcium-based adsorbent cyclic regeneration amount, low overall thermal efficiency and large required gasifier reactor volume.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides a coal gasification hydrogen production method which has high capacity and high hydrogen content in the produced synthesis gas.
In order to achieve the above object, according to one aspect of the present invention, there is provided a coal gasification apparatus comprising an upper stage gasification chamber and a lower stage combustion gasification chamber which are communicated with each other, wherein the upper stage gasification chamber is provided with a synthesis gas outlet, the lower stage gasification chamber is provided with a slag discharge port, and the peripheral wall of the upper stage gasification chamber is provided with upper nozzles which are circumferentially spaced and extend into the upper stage gasification chamber, and the peripheral wall of the lower stage combustion gasification chamber is provided with lower nozzles which are circumferentially spaced and extend into the lower stage combustion gasification chamber, wherein the upper nozzles are capable of injecting steam to generate water gas shift.
Preferably, the number of the upper nozzles and the number of the lower nozzles are more than two and are respectively arranged at equal intervals along the circumferential direction.
Preferably, the upper-stage gasification chamber and the lower-stage combustion gasification chamber are both formed into cylindrical chambers, the plurality of upper nozzles extend into the upper-stage gasification chamber in an eccentric direction deviating from the radial direction of the upper-stage gasification chamber, and the plurality of lower nozzles extend into the lower-stage combustion gasification chamber in an eccentric direction deviating from the radial direction of the lower-stage combustion gasification chamber, so that the injected material can form a vortex flow in the upper-stage gasification chamber and the lower-stage combustion gasification chamber.
Preferably, the eccentric angles of the upper nozzle and the lower nozzle deviating from the radial direction are both 0-30 degrees.
Preferably, the coal gasification apparatus comprises a plurality of said lower stage combustion gasification chambers which are located below said upper stage gasification chambers and communicate with each other, and/or said coal gasification apparatus comprises a plurality of said upper stage gasification chambers which communicate with each other above said lower stage combustion gasification chambers.
Preferably, the coal gasification apparatus further comprises a synthesis gas conduit having a bottom end connected to the synthesis gas outlet of the upper stage gasification chamber.
Preferably, the upper-section gasification chamber and the lower-section combustion gasification chamber are both cylindrical chambers with the diameter D, and the upper-section gasification chamber is connected with the lower-section combustion gasification chamber through a throat section which is radially reduced; wherein the axial height of the lower section combustion gasification chamber is 1D-5D, the axial height of the upper section gasification chamber is 1D-3D, the diameter of the synthesis gas pipeline is 0.05D-0.5D, and the axial height is 1.5D-8D.
Preferably, a CaO adsorbent is further disposed in the upper stage gasification chamber and/or the synthesis gas conduit.
Preferably, the casings of the upper-stage gasification chamber and the lower-stage combustion gasification chamber are vertical cylindrical casings of refractory brick lining structures or water-cooled wall lining structures, the coal gasification device further comprises a pressure vessel casing which is arranged around the outside of the vertical cylindrical casing in a radial spacing mode, and an inert gas plenum chamber is formed between the pressure vessel casing and the vertical cylindrical casing.
According to another aspect of the present invention, there is also provided a method for coal gasification with rich hydrogen production using the coal gasification apparatus, the method comprising: after the lower combustion gasification chamber is preheated, coal fuel and a gasifying agent are introduced into the lower combustion gasification chamber through the lower nozzle to generate combustion and gasification reaction, and water vapor is introduced into the upper gasification chamber through the upper nozzle to generate further water gas shift reaction.
Preferably, the reaction temperature in the lower-section combustion gasification chamber is controlled to be 1200-1400 degrees, and the reaction temperature in the upper-section gasification chamber is controlled to be 700-1000 degrees.
Preferably, the mass ratio of the coal fuel injected by the lower nozzle to the water vapor injected by the upper nozzle is 1: 1.5-2.0.
Preferably, the residence time of the reaction gas in the lower-section combustion gasification chamber is 2-5 seconds, and the residence time of the reaction gas in the upper-section gasification chamber is 2-4 seconds; and the synthesis gas outlet is connected with a synthesis gas pipeline, and the residence time of reaction gas in the synthesis gas pipeline is 1-3 seconds.
According to the technical scheme, the coal gasification device and the coal gasification method thereof adopt the partition gasification to optimize the temperature distribution in the furnace, are suitable for combustion and gasification of coal fuel in the high-temperature lower-stage combustion gasification chamber, and spray high-pressure steam into the relatively low-temperature upper-stage gasification chamber, so that the water gas shift reaction can be enhanced, the hydrogen yield is increased, the hydrogen content in the produced synthesis gas is obviously higher than that of the current mainstream entrained flow gasifier, the load of a downstream shift process can be reduced, and the coal gasification device and the coal gasification method thereof are suitable for a coal chemical process flow taking hydrogen as a final target product.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural view of a coal gasification apparatus according to a preferred embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of the coal gasification apparatus shown in FIG. 1, illustrating the distribution and installation angle of the upper or lower nozzles on the vertical cylindrical casing.
Description of the reference numerals
1 lower section combustion gasification chamber 2 upper section gasification chamber
3 throat section 4 syngas outlet
5 slag bath 6 slag discharging hole
7 vertical cylindrical housing 8a lower nozzle
8b upper nozzle 9 synthesis gas pipeline
10 pressure vessel shell 11 inert gas plenum
H1 axial height a eccentric angle of lower combustion gasification chamber
H2 axial height D diameter of upper gasification chamber
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. 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.
In the present invention, unless otherwise specified, use of the terms of orientation such as "upper, lower, top, bottom" or the like are generally used in the description of the orientation shown in the drawings or the positional relationship of the components with respect to each other in the vertical, or gravitational direction; "vertical direction" means the vertical direction of the drawing sheet, and "horizontal direction" means the horizontal direction of the drawing sheet; "inner and outer" generally refers to the inner and outer of the chamber relative to the chamber or the radially inner and outer relative to the center of the circle.
As shown in fig. 1, the present invention provides a novel coal gasification apparatus, which comprises an upper-stage gasification chamber 2 and a lower-stage combustion gasification chamber 1 that are communicated with each other, wherein the upper-stage gasification chamber 2 is provided with a synthesis gas outlet 4, the lower-stage gasification chamber 1 is provided with a slag bath 5 and a slag discharge port 6, the peripheral wall of the upper-stage gasification chamber 2 is provided with upper nozzles 8b that are circumferentially spaced and extend into the upper-stage gasification chamber 2, and the peripheral wall of the lower-stage combustion gasification chamber 1 is provided with lower nozzles 8a that are circumferentially spaced and extend into the lower-stage combustion gasification chamber 1.
In this coal gasification unit, instead of using a single combustion gasification chamber, zoned gasification is used to optimize the temperature distribution in the furnace. The lower section combustion gasification chamber 1 has higher temperature and can perform combustion gasification reaction of coal fuel, and the upper nozzle 8b can further participate in gasification reaction requiring relatively lower temperature after spraying selectable media so as to meet the process requirement. The lower stage combustion gasification chamber 1 may be a single gasification combustion chamber, or may be a plurality of gasification combustion chambers communicated with each other, and the synthesis gas generated after combustion and gasification reaction in the gasification combustion chamber (synthesis gas mainly containing hydrogen and carbon monoxide generated by reaction of coal and a gasification agent) is entirely fed into the upper stage gasification chamber 2 to perform subsequent reactions, such as water gas shift reaction. Likewise, the upper stage gasification chamber 2 may be single or plural. Furthermore, the biggest difference between the upper stage gasification chamber 2 and the lower stage combustion gasification chamber 1 is that the lower stage combustion gasification chamber 1 is a combustion chamber of coal, and no coal is needed to participate in the upper stage gasification chamber 2.
Further, the upper-section gasification chamber 2 and the lower-section combustion gasification chamber 1 can adopt a multi-stage multi-nozzle design, and the number of nozzles and sprayed materials can be adjusted, so that the overall operation load of the gasification furnace is large in elasticity and flexible to operate.
In the present embodiment, at least one of the plurality of upper nozzles 8b is a steam nozzle capable of injecting steam into the upper-stage gasification chamber 2. This is due to the water gas shift reaction (CO + H) during the coal gasification reaction2O→CO2+H2) Is an important reaction for generating hydrogen, the gasification reaction is an exothermic reaction, and when analyzed from the thermodynamic equilibrium perspective, lowering the temperature and increasing the water-gas ratio will favor the reaction equilibrium moving to the right. Therefore, after high-pressure steam is sprayed into the upper-stage gasification chamber 2, the water gas shift reaction is enhanced, and more hydrogen can be produced. Therefore, the water vapor is sprayed into the upper-section gasification chamber 2, so that the water gas shift reaction can be enhanced, the hydrogen yield is increased, the hydrogen/carbon ratio is flexibly adjusted, and the subsequent process requirements are met. Meanwhile, the temperature of the synthesis gas outlet 4 is reduced, slag entrainment is reduced, and the sensible heat of the coal gas is fully utilized.
Wherein, the upper segment gasification chamber 2 and the lower segment combustion gasification chamber 1 are preferably cylindrical chambers, a plurality of upper nozzles 8b all extend into the upper segment gasification chamber 2 in the radial eccentric direction deviating from the upper segment gasification chamber 2, and a plurality of lower nozzles 8a all extend into the lower segment combustion gasification chamber 1 in the radial eccentric direction deviating from the lower segment combustion gasification chamber 1, so that the sprayed materials can form vortex in the upper segment gasification chamber 2 and the lower segment combustion gasification chamber 1. Therefore, by the eccentric arrangement of the multiple nozzles, a vortex is formed, the spiral residence time of fuel particles in the furnace is prolonged, the direct impact of flame among the nozzles is reduced, the burning loss of the nozzles is avoided, the service life of the nozzles is prolonged, and the performance of the device is improved.
Specifically, in the present embodiment as shown in fig. 2, each of the upper nozzles 8b and the lower nozzles 8a is larger than two (4 as illustrated) and arranged at equal intervals in the circumferential direction, respectively. The eccentric angles a of the upper nozzle 8b and the lower nozzle 8a deviating from the radial direction are preferably 0-30 degrees so as to form large-size vortex or impinging flow around the inner wall of the vertical cylindrical shell 7, strengthen the mixing process of coal fuel particles and gasifying agents or water vapor and the like and improve the retention time of the fuel particles in the furnace, thereby achieving good process and engineering effects and achieving the advantages of high effective gas components, high carbon conversion rate and long service life of the refractory lining of the furnace wall.
Further, the coal gasification apparatus of the present invention preferably further comprises a synthesis gas pipe 9, and the bottom end of the synthesis gas pipe 9 is connected to the synthesis gas outlet 4 of the upper stage gasification chamber 2. The syngas exiting the syngas outlet 4 may further generate a small amount of gasification reaction in the long length of syngas conduit 9, thereby increasing the hydrogen production.
Preferably, CaO sorbents may also be provided in the upper stage gasification chamber 2 and/or the synthesis gas conduit 9. The final hydrogen purity is improved by absorbing carbon dioxide and the like, which are main components in the synthesis gas, with a CaO adsorbent and the like. For example, sieve plates may be provided at both ends of the synthesis gas conduit 9, with CaO adsorbent such as calcium oxide particles being filled between the sieve plates, and the synthesis gas entering the synthesis gas conduit through the sieve holes comes into contact with the calcium oxide particles as it flows upward. It will be appreciated by those skilled in the art that other means, such as passing the syngas through a lime water spray tower to remove CO, may also be used2And further, a synthesis gas having a high hydrogen/carbon ratio is obtained by membrane separation. In the present embodiment, it is more preferable that the upper stage gasification chamber 2 or the synthesis gas pipe 9 be detachably provided in a two-stage structure in order to facilitate installation or maintenance of the CaO adsorbent.
Referring to fig. 1, the upper stage gasification chamber 2 and the lower stage combustion gasification chamber 1 are preferably cylindrical chambers each having a diameter D, and the upper stage gasification chamber 2 and the lower stage combustion gasification chamber 1 are connected by a radially reduced throat section 3 to separate each other and enhance residence time of the vortex in each gasification chamber. Among them, the axial height H1 of the lower stage combustion gasification chamber 1 is determined according to the flame temperature generated by the combustion reaction, and the like, and generally 1D to 5D is preferable, and correspondingly, the axial height H2 of the upper stage gasification chamber 2 is preferably 1D to 3D, the diameter of the synthesis gas conduit 9 is preferably 0.05D to 0.5D, and the axial height is preferably 1.5D to 8D. The preferable size proportion of each reaction chamber aims to optimize the internal flow field and the reaction residence time, so that rotational flow is formed in the reaction chamber, and the slag is brought to the side wall of the gasification chamber by using the centrifugal force generated by the rotational flow to form a slag layer protector wall with a certain thickness. In addition, the lengths of the lower combustion gasification chamber 1, the upper combustion gasification chamber 2 and the synthesis gas conduit 9 should satisfy the following requirements when the coal gasification reaction is performed: the residence time of the reaction gas in the lower-section combustion gasification chamber 1 is about 2-5 seconds, and the residence time of the reaction gas in the upper-section gasification chamber 2 is about 2-4 seconds; and the residence time of the synthesis gas in the synthesis gas conduit 9 is about 1-3 seconds. This residence time design ensures sufficient carbon burnout and water gas shift reaction. Of course, the size of the above pipe chambers is not limited to this, and can be adjusted accordingly according to different process requirements.
In the present embodiment, the casings of the upper-stage gasification chamber 2 and the lower-stage combustion gasification chamber 1 are preferably vertical cylindrical casings 7 of a refractory brick lining structure or a water-cooled wall lining structure, pressure vessel casings 10 are arranged around the outside of the vertical cylindrical casings 7 at intervals in the radial direction, and an inert gas plenum chamber 11 is formed between the pressure vessel casings 10 and the vertical cylindrical casings 7 so as to ensure the balance of the internal pressure and the external pressure of the vertical cylindrical casings 7, i.e. to protect the vertical cylindrical casings 7 from being pressed, and to transfer the pressure to the pressure vessel casings 10 so as to enable the pressure vessel casings to bear the internal and external pressure difference of about 2-6.5 MPa.
According to the coal gasification apparatus described above, a method for gasification of coal with rich hydrogen production using the coal gasification apparatus shown in fig. 1 will be described below, the method including: after the lower combustion gasification chamber 1 is preheated, coal fuel and gasification agent are introduced into the lower combustion gasification chamber 1 through the lower nozzle 8a to generate combustion and gasification reaction, and steam is introduced into the upper combustion gasification chamber 2 through the upper nozzle 8b to generate further water gas shift reaction.
Carbon-containing fuel (such as dry coal powder) and gasifying agent (oxygen) are sprayed into a lower-section combustion gasification chamber 1 of the coal gasification device from a lower nozzle 8a through a conveying system; high-pressure steam is injected from the upper nozzle 8b into the upper-stage gasification chamber 2.
The reaction process of the carbonaceous material in the coal gasification device is mainly divided into the following stages:
1) the fuel and the oxygen generate high-temperature reaction which mainly takes combustion and is accompanied with gasification in the lower-section combustion gasification chamber 1, the reaction temperature can reach 1200-1400 ℃ or even above, the slag discharge temperature is higher than the melting point of the fuel ash and forms flowing state ash slag to be discharged to a bottom slag pool 5, high-temperature flue gas generated by the reaction flows upwards to enter an upper-section gasification chamber 2, fuel particles form a vortex flow field in the furnace along with airflow, and the retention time of the particles is prolonged;
2) high-pressure superheated steam at about 300 ℃ is sent into the upper-stage gasification chamber 2 from four upper nozzles 8b of the upper-stage gasification chamber 2 to form a vortex flow field, is mixed with high-temperature flue gas generated from the lower-stage combustion gasification chamber 1 and unburnt particles, generates gasification reaction mainly comprising water gas shift reaction and reforming reaction, and controls the reaction temperature in the upper-stage gasification chamber 2 to be about 700-1000 ℃;
3) and large particles which are not burnt out in the upper-stage gasification chamber 2 fall downwards into the lower-stage combustion gasification chamber 1 to perform a reaction mainly based on combustion due to the action of gravity and the like, and the contained carbon residues are completely burnt out. The fine fly ash particles flow upwards along with the airflow and flow out from the synthesis gas outlet 4 at the upper part together with the synthesis gas;
4) in the inner space of the synthesis gas pipe 9 having a relatively low temperature in the upper part of the coal gasification apparatus, a small amount of gasification and shift reaction may also occur, further increasing the content of hydrogen in the synthesis gas.
The two-section reaction partition is adopted, and the high-temperature combustion reaction and the gasification reaction are reasonably organized in the coal gasification device, so that the overall carbon conversion rate, the cold coal gas efficiency and the like of the coal gasification device are greatly improved, the temperature in the furnace is reasonably optimized, the hydrogen content in the final synthesis gas product is obviously improved, and the method is very suitable for the large-scale coal chemical industry process taking hydrogen as a target product.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
With the coal gasification apparatus shown in fig. 1 and 2, the coal fuel injected by the lower nozzle 8a is dry pulverized coal and pure oxygen, and the high-pressure superheated steam at 300 ℃ is injected by the upper nozzle 8 b.
Wherein the oxygen-coal ratio is 0.78, the steam-coal ratio is 2, and the steam-coal ratio (mass ratio) between the coal fuel injected from the lower nozzle 8a and the water vapor injected from the upper nozzle 8b is preferably 1:1.5-2.0, which generally enables the temperature in the upper stage gasification chamber 2 to be between 650 and 950 ℃.
The detection result shows that: the carbon conversion in the lower stage combustion gasification chamber 1 was 98%, and the carbon conversion in the upper stage gasification chamber 2 was 99%.
Wherein the reaction temperature of the lower gasification chamber 1 is 1401 ℃, and the composition of the synthesis gas discharged from the lower gasification chamber 1 to the upper gasification chamber 2 is shown in table 1.
Table 1: composition of syngas discharged from the lower stage gasification chamber 1
The reaction temperature in the upper stage gasification chamber 2 is 928 ℃, and the composition of the synthesis gas flowing out of the synthesis gas outlet 4 is shown in Table 2.
Table 2: composition of the syngas discharged at syngas outlet 4
Synthesis gas composition (dry basis) | |
N2 | 7.9% |
H2 | 41.5% |
CO | 17.5% |
CO2 | 30.0% |
H2S | 0.1% |
CH4 | 2.9% |
In the synthesis gas finally produced by the coal gasification device, H2Is more than 40 percent, while H in the synthesis gas produced by dry coal powder gasification in a common gasification furnace2The content is generally not higher than 30%, so the coal gasification device and the coal gasification method thereof can greatly improve the hydrogen content of the final synthesis gas.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the scope of the technical idea of the present invention, which does not exceed the idea of the present invention, and thus fall within the scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A coal gasification device utilized by the coal gasification hydrogen production method comprises an upper-stage gasification chamber (2) and a lower-stage combustion gasification chamber (1) which are communicated with each other, wherein the upper-stage gasification chamber (2) is provided with a synthesis gas outlet (4), the lower-stage gasification chamber (1) is provided with a slag discharge port (6), an upper nozzle (8b) extending into the upper-stage gasification chamber (2) is arranged on the peripheral wall of the upper-stage gasification chamber (2), lower nozzles (8a) which are circumferentially arranged at intervals and extend into the lower-stage combustion gasification chamber (1) are arranged on the peripheral wall of the lower-stage combustion gasification chamber (1), and the upper nozzle (8b) can be used for spraying water vapor, and the coal gasification hydrogen production method is characterized by comprising the following steps: after the lower-section combustion gasification chamber (1) is preheated, introducing coal fuel and a gasification agent into the lower-section combustion gasification chamber (1) through the lower nozzle (8a) to generate combustion and gasification reaction, and introducing water vapor into the upper-section gasification chamber (2) through the upper nozzle (8b) to generate further water gas shift reaction, wherein the lower-section combustion gasification chamber (1) is a combustion chamber of coal, and the upper-section gasification chamber (2) does not need coal to participate.
2. The coal gasification hydrogen production method according to claim 1, wherein the reaction temperature in the lower combustion gasification chamber (1) is controlled to be 1200 ° to 1400 °, and the reaction temperature in the upper combustion gasification chamber (2) is controlled to be 700 ° to 1000 °.
3. The coal gasification hydrogen production method according to claim 1, wherein the mass ratio of the coal fuel injected by the lower nozzle (8a) to the water vapor injected by the upper nozzle (8b) is 1: 1.5-2.0.
4. The coal gasification hydrogen production method according to claim 1, wherein the residence time of the reaction gas in the lower stage combustion gasification chamber (1) is 2 to 5 seconds, and the residence time of the reaction gas in the upper stage gasification chamber (2) is 2 to 4 seconds; and the synthetic gas outlet (4) is connected with a synthetic gas pipeline (9), and the residence time of the reaction gas in the synthetic gas pipeline (9) is 1-3 seconds.
5. The coal gasification hydrogen production method according to claim 1, wherein the number of the upper nozzles (8b) and the number of the lower nozzles (8a) are larger than two and are respectively arranged at equal intervals in the circumferential direction.
6. The coal gasification hydrogen production method according to claim 5, wherein the upper stage gasification chamber (2) and the lower stage combustion gasification chamber (1) are formed into cylindrical chambers, a plurality of upper nozzles (8b) extend into the upper stage gasification chamber (2) in an eccentric direction deviating from the radial direction of the upper stage gasification chamber (2), and a plurality of lower nozzles (8a) extend into the lower stage combustion gasification chamber (1) in an eccentric direction deviating from the radial direction of the lower stage combustion gasification chamber (1), so that the injected material can form a vortex flow in the upper stage gasification chamber (2) and the lower stage combustion gasification chamber (1).
7. The coal gasification hydrogen production method according to claim 6, wherein the eccentric angles (a) of the upper nozzle (8b) and the lower nozzle (8a) deviated from the radial direction are both 0-30 °.
8. The coal gasification hydrogen production method according to claim 1, wherein the coal gasification apparatus comprises a plurality of lower stage combustion gasification chambers (1) which are located below the upper stage gasification chambers (2) and are communicated with each other, and/or the coal gasification apparatus comprises a plurality of upper stage gasification chambers (2) which are communicated with each other above the lower stage combustion gasification chambers (1).
9. The coal gasification hydrogen production method according to claim 1, wherein the coal gasification apparatus further comprises a synthesis gas pipe (9), and the bottom end of the synthesis gas pipe (9) is connected to the synthesis gas outlet (4) of the upper stage gasification chamber (2).
10. The coal gasification hydrogen production method according to claim 9, wherein the upper stage gasification chamber (2) and the lower stage combustion gasification chamber (1) are both cylindrical chambers with the diameter D, and the upper stage gasification chamber (2) and the lower stage combustion gasification chamber (1) are connected through a throat section (3) which is radially reduced;
wherein the axial height of the lower section combustion gasification chamber (1) is 1D-5D, the axial height of the upper section gasification chamber (2) is 1D-3D, the diameter of the synthesis gas pipeline (9) is 0.05D-0.5D, and the axial height is 1.5D-8D.
11. The coal gasification hydrogen production method according to claim 9, wherein a CaO adsorbent is further arranged in the upper stage gasification chamber (2) and/or the synthesis gas pipeline (9).
12. The coal gasification hydrogen production method according to claim 9, wherein the casings of the upper stage gasification chamber (2) and the lower stage combustion gasification chamber (1) are vertical cylindrical casings (7) with refractory brick lining structure or water wall lining structure, the coal gasification device further comprises a pressure vessel casing (10) arranged around the outside of the vertical cylindrical casing (7) at a radial interval, and an inert gas plenum chamber (11) is formed between the pressure vessel casing (10) and the vertical cylindrical casing (7).
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