CN108192649B - Process system for directly producing hydrogen based on coke oven and control method thereof - Google Patents
Process system for directly producing hydrogen based on coke oven and control method thereof Download PDFInfo
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- CN108192649B CN108192649B CN201810104747.XA CN201810104747A CN108192649B CN 108192649 B CN108192649 B CN 108192649B CN 201810104747 A CN201810104747 A CN 201810104747A CN 108192649 B CN108192649 B CN 108192649B
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000001257 hydrogen Substances 0.000 title claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 67
- 239000000571 coke Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000011084 recovery Methods 0.000 claims abstract description 47
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003245 coal Substances 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 28
- 239000003034 coal gas Substances 0.000 claims abstract description 27
- 238000000746 purification Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 homologues Chemical compound 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 108010004350 tyrosine-rich amelogenin polypeptide Proteins 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/18—Modifying the properties of the distillation gases in the oven
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- 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
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
-
- 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
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/028—Dust removal by electrostatic precipitation
-
- 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
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
- C10K1/046—Reducing the tar content
-
- 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
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses a process system for directly producing hydrogen based on a coke oven, which comprises the following steps: the device comprises a vertical pipe, a three-way valve, a coal gas recovery and purification branch and a hydrogen recovery branch which are connected with the three-way valve, wherein the vertical pipe is positioned at the top of the carbonization chamber, an ammonia water spraying device is arranged on the vertical pipe, and the three-way valve is arranged at the outlet of the vertical pipe; the coal gas recovery and purification branch comprises a first gas collecting pipe, a primary cooler, a first electric coke catcher, a desulfurizing tower, a first ammonia washing tower and a benzene washing tower which are connected in sequence; the hydrogen recovery branch comprises a second gas collecting pipe, a second ammonia washing tower and a second electric coke catcher which are sequentially connected; when the temperature of the central coal of the carbonization chamber is less than or equal to the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the coal gas recovery and purification branch; and when the temperature of the central coal of the carbonization chamber is higher than the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the hydrogen recovery branch. The process system for directly producing hydrogen based on the coke oven reduces the cost of recovering hydrogen in coke oven gas.
Description
Technical Field
The invention relates to the technical field of coke oven gas treatment, in particular to a process system for directly producing hydrogen based on a coke oven and a control method thereof.
Background
The coke oven is a furnace for heating and dry distilling coal to generate coke under the condition of isolating air, the coal generates coke oven gas simultaneously in the dry distilling process, and the main component of the coke oven gas is H2(55% ~ 60) and CH4(23% ~ 27%), and further contains a small amount of CO (5% ~ 8%), C2The above unsaturated hydrocarbons (2% ~ 4%), CO2（1.5%~3%)、O2(0.3%~0.8%))、N2(3% ~ 7%), etc., the coke oven gas belongs to medium heat value gas, and the heat value is 17 ~ 19MJ/Nm3Is an important secondary energy source. The coke oven gas has high hydrogen content, and can generate high-purity hydrogen through pressure swing adsorption, the hydrogen is a clean new energy fuel and can also be used as a raw material for synthesizing ammonia, and the hydrogen used by a steel plant is used as a protective gas for bright annealing of steel rolling.
Raw coke oven gas initially generated by a coke oven contains various impurities such as tar, benzene, naphthalene, sulfide, ammonia, hydrogen hydride and the like, and clean coke oven gas can be obtained only through a plurality of procedures such as primary cooling, desulfurization, deamination, debenzolization and the like, and is used as a raw material for preparing hydrogen through pressure swing adsorption. However, at present, high-purity hydrogen is generated by clean coke oven gas, and the cost is high.
Disclosure of Invention
The invention mainly aims to provide a process system for directly producing hydrogen based on a coke oven and a control method thereof, and aims to reduce the cost of recovering hydrogen in coke oven gas.
In order to achieve the aim, the invention provides a process system for directly producing hydrogen based on a coke oven, which comprises the following steps: a vertical pipe, a three-way valve, a coal gas recovery and purification branch and a hydrogen recovery branch which are connected with the three-way valve, wherein,
the vertical pipe is positioned at the top of the carbonization chamber, the ammonia water spraying device is arranged on the vertical pipe, and the three-way valve is arranged at the outlet of the vertical pipe;
the coal gas recovery and purification branch comprises a first gas collecting pipe, a primary cooler, a first electric coke catcher, a desulfurization tower, a first ammonia washing tower and a benzene washing tower which are connected in sequence;
the hydrogen recovery branch comprises a second gas collecting pipe, a second ammonia washing tower and a second electric coke catcher which are sequentially connected;
when the temperature of the central coal of the carbonization chamber is less than or equal to the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the coal gas recovery and purification branch; and when the temperature of the central coal of the carbonization chamber is higher than the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the hydrogen recovery branch.
Preferably, a first air blower is arranged between the first electric coke-capturing and desulfurizing tower of the coal gas recovery and purification branch.
Preferably, a second air blower is arranged behind the second electric coke catching of the hydrogen recovery branch.
Preferably, the first ammonia washing tower and the second ammonia washing tower are both connected with an ammonia still.
Preferably, the process system for directly producing hydrogen based on the coke oven further comprises a controller electrically connected with the three-way valve, a temperature measuring device for measuring the temperature of the central coal of the carbonization chamber is arranged in the carbonization chamber, and the controller is electrically connected with the temperature measuring device.
The invention further provides a control method of a process system for directly producing hydrogen based on the coke oven, which comprises the following steps:
in the initial stage of coal carbonization, controlling a three-way valve to enable a vertical pipe to be communicated with a coal gas recovery and purification branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, entering the coal gas recovery and purification branch to be sequentially subjected to cooling, tar removal, desulfurization, ammonia removal and benzene removal treatment to obtain clean coal gas;
and when the temperature of the central coal of the carbonization chamber exceeds the preset temperature, controlling the three-way valve to switch to enable the vertical pipe to be communicated with the hydrogen recovery branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, removing ammonia through a second ammonia washing tower of the hydrogen recovery branch to obtain high-concentration hydrogen.
Preferably, the preset temperature is 750 ℃. (the set temperature is about 750 ℃ for a general blended coal, depending on the coal type).
The process system for directly producing hydrogen based on the coke oven has the following beneficial effects:
1. the coke oven can directly produce coke oven gas and hydrogen with the concentration higher than 95 percent at the same time, and the cost for recovering the hydrogen is low;
2. the gas cooler of the original system can be eliminated while the dust removal efficiency and the dust removal stability of the electrostatic dust collector are ensured, so that the system is simplified.
Drawings
FIG. 1 is a schematic structural diagram of a process system for directly producing hydrogen based on a coke oven.
In the figure, 10-vertical pipe, 20-three-way valve, 31-first gas collecting pipe, 32-primary cooler, 33-first electric coke-capturing, 34-desulfurizing tower, 35-first ammonia washing tower, 36-benzene washing tower, 37-first blower, 41-second gas collecting pipe, 42-second ammonia washing tower, 43-second electric coke-capturing, 44-second blower and 50-ammonia still.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a process system for directly producing hydrogen based on a coke oven.
In the preferred embodiment, a process system for directly producing hydrogen based on a coke oven comprises: a vertical pipe 10, a three-way valve 20, and a coal gas recovery purification branch and a hydrogen gas recovery branch connected with the three-way valve 20, wherein,
the vertical pipe 10 is positioned at the top of the carbonization chamber, the ammonia spray device is arranged on the vertical pipe 10, and the three-way valve 20 is arranged at the outlet of the vertical pipe 10;
the coal gas recovery and purification branch comprises a first gas collecting pipe 31, a primary cooler 32, a first electric tar precipitator 33, a desulfurizing tower 34, a first ammonia washing tower 35 and a benzene washing tower 36 which are connected in sequence;
the hydrogen recovery branch comprises a second gas collecting pipe 41, a second ammonia washing tower 42 and a second electric coke catcher 43 which are connected in sequence;
when the temperature of the central coal of the carbonization chamber is less than or equal to the preset temperature, controlling the three-way valve 20 to enable the vertical pipe 10 to be communicated with the coal gas recovery and purification branch; when the temperature of the coal at the center of the carbonization chamber is higher than the preset temperature, the three-way valve 20 is controlled to communicate the vertical pipe 10 with the hydrogen recovery branch.
Further, a first blower 37 is arranged between the first electric coke-capturing 33 and the desulfurizing tower 34 of the coal gas recovery and purification branch. A second blower 44 is provided behind the second electrical trap 43 of the hydrogen recovery branch.
The first ammonia washing tower 35 and the second ammonia washing tower 42 are both connected with an ammonia still 50. The ammonia water in the ammonia scrubber is recovered by an ammonia still 50.
Further, the process system for directly producing hydrogen based on the coke oven further comprises a controller electrically connected with the three-way valve 20, a temperature measuring device for measuring the temperature of the central coal of the carbonization chamber is arranged in the carbonization chamber, and the controller is electrically connected with the temperature measuring device.
Through setting up the controller to realize automatic control switching, reduced manual operation. Because the temperature of the dry distillation coal is continuously increased from two sides to the center, when the temperature of the coal in the center of the carbonization chamber reaches 750 ℃, the three-way valve is switched to the hydrogen recovery branch.
The coke oven is formed by connecting a plurality of groups of carbonization chambers in parallel, each carbonization chamber is mutually independent, the dry distillation time of coal in the carbonization chambers is about 18-22h, the coal mainly generates methane, hydrogen sulfide, tar, benzene, homologues, naphthalene and the like in the initial stage of dry distillation, the content of hydrogen is continuously increased along with the increase of the dry distillation temperature, and almost all the hydrogen released by the coal in the coking process in the later stage of dry distillation is hydrogen. Therefore, the process system for directly producing hydrogen based on the coke oven can be switched in time according to the temperature of the central coal of the coking chamber.
The working principle of the process system for directly producing hydrogen based on the coke oven is as follows.
In the initial stage of coal carbonization, the three-way valve 20 is controlled to enable the vertical pipe 10 to be communicated with the coal gas recovery and purification branch, and the coke oven gas is sprayed with ammonia water through the vertical pipe 10 to be cooled and then enters the coal gas recovery and purification branch to be sequentially subjected to cooling, tar removal, desulfurization, ammonia removal and benzene removal treatment to obtain clean coal gas;
when the temperature of the central coal of the carbonization chamber exceeds the preset temperature (750 ℃), the three-way valve 20 is controlled to be switched to enable the vertical pipe 10 to be communicated with the hydrogen recovery branch, and after the coke oven gas is sprayed with ammonia water through the vertical pipe 10 to be cooled, the ammonia is removed through the second ammonia washing tower 42 of the hydrogen recovery branch to obtain high-concentration hydrogen.
The process system for directly producing hydrogen based on the coke oven has the following beneficial effects:
1. the coke oven can directly produce coke oven gas and hydrogen with the concentration higher than 95 percent at the same time, and the cost for recovering the hydrogen is low;
2. the gas cooler of the original system can be eliminated while the dust removal efficiency and the dust removal stability of the electrostatic dust collector are ensured, so that the system is simplified.
The invention further provides a control method of the process system for directly producing hydrogen based on the coke oven.
In the preferred embodiment, the control method of the process system for directly producing hydrogen based on the coke oven comprises the following steps:
in the initial stage of coal carbonization, controlling a three-way valve to enable a vertical pipe to be communicated with a coal gas recovery and purification branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, entering the coal gas recovery and purification branch to be sequentially subjected to cooling, tar removal, desulfurization, ammonia removal and benzene removal treatment to obtain clean coal gas;
and when the temperature of the central coal of the carbonization chamber exceeds the preset temperature, controlling the three-way valve to switch to enable the vertical pipe to be communicated with the hydrogen recovery branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, removing ammonia through a second ammonia washing tower of the hydrogen recovery branch to obtain high-concentration hydrogen.
Specifically, the preset temperature is 750 ℃. (the set temperature is about 750 ℃ for a general blended coal, depending on the coal type).
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or any other related technical fields, are intended to be covered by the scope of the present invention.
Claims (7)
1. A process system for directly producing hydrogen based on a coke oven is characterized by comprising the following steps: a vertical pipe, a three-way valve, a coal gas recovery and purification branch and a hydrogen recovery branch which are connected with the three-way valve, wherein,
the vertical pipe is positioned at the top of the carbonization chamber, the ammonia water spraying device is arranged on the vertical pipe, and the three-way valve is arranged at the outlet of the vertical pipe;
the coal gas recovery and purification branch comprises a first gas collecting pipe, a primary cooler, a first electric coke catcher, a desulfurization tower, a first ammonia washing tower and a benzene washing tower which are connected in sequence;
the hydrogen recovery branch comprises a second gas collecting pipe, a second ammonia washing tower and a second electric coke catcher which are sequentially connected;
when the temperature of the central coal of the carbonization chamber is less than or equal to the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the coal gas recovery and purification branch; and when the temperature of the central coal of the carbonization chamber is higher than the preset temperature, controlling the three-way valve to enable the vertical pipe to be communicated with the hydrogen recovery branch.
2. The coke oven-based process system for directly producing hydrogen of claim 1, wherein a first blower is arranged between the first electric coke-capturing and desulfurizing tower of the coal gas recovery and purification branch.
3. The coke oven based process system for directly producing hydrogen of claim 1, wherein a second blower is disposed behind the second electrical char capture of the hydrogen recovery branch.
4. The coke oven-based process system for directly producing hydrogen of claim 1, wherein the first ammonia scrubber and the second ammonia scrubber are both connected to an ammonia still.
5. The coke oven-based process system for directly producing hydrogen according to any one of claims 1 to 4, further comprising a controller electrically connected with the three-way valve, wherein a temperature measuring device for measuring the temperature of coal at the center of the coking chamber is arranged in the coking chamber, and the controller is electrically connected with the temperature measuring device.
6. The control method of the process system for directly producing hydrogen based on the coke oven according to any one of the claims 1 to 5, characterized by comprising the following steps:
in the initial stage of coal carbonization, controlling a three-way valve to enable a vertical pipe to be communicated with a coal gas recovery and purification branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, entering the coal gas recovery and purification branch to be sequentially subjected to cooling, tar removal, desulfurization, ammonia removal and benzene removal treatment to obtain clean coal gas;
and when the temperature of the central coal of the carbonization chamber exceeds the preset temperature, controlling the three-way valve to switch to enable the vertical pipe to be communicated with the hydrogen recovery branch, and after the coke oven gas is cooled by spraying ammonia water through the vertical pipe, removing ammonia through a second ammonia washing tower of the hydrogen recovery branch to obtain high-concentration hydrogen.
7. The method of claim 6, wherein the preset temperature is 750 ℃.
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| JP2002069456A (en) * | 2000-08-31 | 2002-03-08 | Kawasaki Steel Corp | Method for recovering sensible heat of coke oven gas |
| US7662435B2 (en) * | 2003-11-12 | 2010-02-16 | Intelligent Energy, Inc. | Method for reducing coking in a hydrogen generation reactor chamber |
| CN101701703B (en) * | 2009-11-25 | 2011-07-06 | 中冶焦耐工程技术有限公司 | Residual heat utilizing technology of coke oven crude gas |
| CN101850949B (en) * | 2010-06-11 | 2012-05-23 | 大连理工大学 | Method with high purity and high recovery rate for purifying hydrogen gas in coke oven gas |
| US9315452B2 (en) * | 2011-09-08 | 2016-04-19 | Expander Energy Inc. | Process for co-producing commercially valuable products from byproducts of fischer-tropsch process for hydrocarbon fuel formulation in a GTL environment |
| CN102517043A (en) * | 2011-11-12 | 2012-06-27 | 太原煤气化股份有限公司 | Method for heating and controlling temperature of coke oven |
| JP6149821B2 (en) * | 2014-08-04 | 2017-06-21 | Ｊｆｅスチール株式会社 | Coke oven gas purification method |
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