CN114348962A - Method for recovering and extracting hydrogen based on discharged torch waste gas - Google Patents
Method for recovering and extracting hydrogen based on discharged torch waste gas Download PDFInfo
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- CN114348962A CN114348962A CN202111591463.6A CN202111591463A CN114348962A CN 114348962 A CN114348962 A CN 114348962A CN 202111591463 A CN202111591463 A CN 202111591463A CN 114348962 A CN114348962 A CN 114348962A
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- 239000002912 waste gas Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005262 decarbonization Methods 0.000 claims abstract description 9
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000005261 decarburization Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 230000009466 transformation Effects 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 230000000149 penetrating effect Effects 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to a method for recovering and extracting hydrogen based on discharged torch waste gas, which comprises the following steps of 1) transformation: carrying out conversion treatment on the waste gas by using a sulfur-tolerant cobalt rod-on-shift catalyst, mixing steam and the waste gas in a mixing tank, then introducing the mixture into a conversion bed for conversion reaction, and converting CO into hydrogen through the conversion reaction; 2) decarbonization: decarbonizing in an adsorption bed, removing most of ineffective components in the converted gas, and performing high-pressure adsorption and low-pressure desorption; 3) separation and purification: and (3) separating the waste gas after decarburization, adopting a single-bed adsorption procedure, and filling adsorbents of activated alumina, activated carbon and a molecular sieve in an adsorption bed. The method has no raw material cost, and uses a novel catalyst and an adsorbent according to the composition of the waste gas to extract the hydrogen with the purity of more than or equal to 99.8 percent. The running cost of the production line is reduced, and the C emission content and the comprehensive energy consumption of the production line are reduced. The economic and social benefits are remarkable.
Description
Technical Field
The invention belongs to the technical field of waste gas recovery, and particularly relates to a method for recovering and extracting hydrogen based on discharged torch waste gas.
Background
At present, most of domestic waste gas treatment modes of PSA separation and purification output are torch combustion discharge, only few enterprises recover waste gas, but the recovery effect is not ideal, and the recovery rate is not 50%. The combustion emission of PSA waste gas not only causes the waste of effective components in the waste gas, but also increases the emission content of C in the atmosphere by the CO2 discharged by combustion, and causes adverse effect on the atmospheric environment.
At present, the waste gas treatment mode of PSA (pressure swing adsorption) output by the silver gathering company of the applicant is two ways of steam boiler recovery and torch combustion discharge, and 70% of waste gas is discharged in a torch combustion mode due to the limited waste gas recovery capacity of the steam boiler, so that physical and psychological health of staff and surrounding residents is harmed, and high-quality sustainable development of enterprises is restricted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recovering and extracting hydrogen based on discharged flare waste gas.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for recovering and extracting hydrogen based on discharged flare waste gas is characterized in that: the method comprises the following specific steps:
1) and (3) transformation: performing conversion treatment on the waste gas by using a sulfur-tolerant cobalt rod-shift catalyst, wherein the content of CO in the recovered waste gas is calculated according to 30 percent, the proportion of steam to the waste gas is controlled to be 0.30-0.40, the steam and the waste gas are mixed in a mixing tank and then enter a conversion bed for conversion reaction, the inlet temperature of the conversion bed is controlled to be 220 ℃ and the bed reaction temperature is controlled to be 450 ℃ respectively, and CO is converted into hydrogen through the conversion reaction;
2) decarbonization: the waste gas after the conversion enters an adsorption bed for decarburization, and most of ineffective components CO in the gas after the conversion are removed2And N2High-pressure adsorption and low-pressure desorption; the adsorption bed adopts a single-bed adsorption process, and the adsorbent adopts activated alumina and silica gel;
3) separation and purification: for H in the waste gas after decarburization2And CO2、CO、CH4、N2Separating by adopting a single-bed adsorption procedure, and filling adsorbents of activated alumina, activated carbon and molecular sieve in the adsorption bed.
Step 2) the adsorbent in the adsorbent bed is filled according to the mass ratio: 4-6% of lower active alumina and 94-96% of upper silica gel.
Step 3) the adsorbent in the adsorbent bed is filled according to the mass ratio: 4-5% of activated alumina at the lowest layer, 12-15% of activated carbon at the middle layer and 80-84% of molecular sieve at the upper layer.
The single-bed adsorption process in the step 2) comprises the following steps: 6-1-3/V flow: the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and evacuation regeneration processes; each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), reverse pressure relief (D), evacuation (V), 3 rd stage pressure equalization rise (E3R), 2 nd stage pressure equalization rise (E2R), 1 st stage pressure equalization rise (E1R) and final pressure rise (FR); each adsorption tower is operated circularly and alternately according to a set time sequence, and adsorption penetrating gas is continuously output from the top of the adsorption tower; the desorption gas in the reverse discharging and evacuating steps is discharged from the bottom of the tower and is sent out of the battery limit zone under the pressure of about 0.02MPa (G), the adsorption temperature is controlled to be 15-40 ℃, and the adsorption pressure is controlled to be 0.5-0.7 MPa.
The single-bed adsorption procedure in the step 3) is a 6-1-3/P process; the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and flushing regeneration processes. In the pressure swing adsorption system, 1 adsorption tower is always in the adsorption step at any moment, pressurized decarbonization gas is introduced from an inlet end, adsorption penetrating gas (namely product hydrogen) is output from an outlet end, and the rest adsorption towers are in different regeneration stages; each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), forward pressure relief (PP), reverse pressure relief (D), flushing (P), 3 rd stage pressure equalization increase (E3R), 2 nd stage pressure equalization increase (E2R), 1 st stage pressure equalization increase (E1R) and final pressure increase (FR); each adsorption tower is operated circularly and alternately according to a set time sequence, adsorption penetrating gas is continuously output from the top of the adsorption tower and is sent to a hydrogen buffer tank to be buffered as product gas under the pressure of 1.25MPa (G) and then is sent out of a boundary area. The stripping gas from the reverse-discharge and flushing steps is discharged from the bottom of the column and is conveyed out of the battery limit at a pressure of about 0.02MPa (G). The adsorption temperature is controlled at 15-40 deg.C, and the adsorption pressure is controlled at 1.1-1.3 MPa.
The invention has the following advantages: the method has no raw material cost, and uses a novel catalyst and an adsorbent according to the composition of the waste gas to transform, separate and purify the waste gas discharged from the torch, so as to extract the hydrogen with the purity of more than or equal to 99.8 percent. The running cost of the production line is reduced, and the C emission content and the comprehensive energy consumption of the production line are reduced. The economic and social benefits are remarkable.
Detailed Description
Embodiment 1, a method for recovering and extracting hydrogen based on discharging flare waste gas, characterized in that: the method comprises the following specific steps:
1) and (3) transformation: according to the composition (CO, H) of the recovered waste gas2、CO2、CH4、N2、O2) Using special sulfur-resistant cobalt catalyst to make conversion treatment, using 30% of CO content in recovered waste gas and controlling steam-waste gas ratio to be 0.30-0.40, mixing the steam and waste gas in mixing tank, then feeding them into conversion bed to make conversion reaction (CO + H)2O＝CO2+H2) The inlet temperature of the conversion bed is controlled to be about 200 ℃, the reaction temperature of the bed layer is controlled to be 200-450 ℃, CO is converted into hydrogen through the conversion reaction, and the CO conversion efficiency reaches more than 99.0 percent.
2) Decarbonization: decarbonizing the waste gas after transformation, selecting activated alumina and silica gel as adsorbents according to the components of the waste gas, loading 4-6% of activated alumina and 94-96% of silica gel on the lower layer of an adsorption bed, adopting the principles of high-pressure adsorption and low-pressure desorption for adsorption, and adopting a single-bed adsorption process of a decarbonization system, namely a 6-1-3/V process: the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and evacuation regeneration processes. In the pressure swing adsorption system, 1 adsorption tower is always in the adsorption step at any moment, raw gas is introduced from an inlet end, adsorption penetrating gas, namely decarbonization gas, is output from an outlet end, and the rest adsorption towers are in different regeneration stages. Each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), reverse pressure relief (D), evacuation (V), 3 rd stage pressure equalization rise (E3R), 2 nd stage pressure equalization rise (E2R), 1 st stage pressure equalization rise (E1R), final pressure rise (FR) and the like. Each adsorption tower is operated circularly and alternately according to a set time sequence, and adsorption penetrating gas is continuously output from the top of the adsorption tower. The desorption gas in the reverse discharging and evacuating steps is discharged from the bottom of the tower, the desorption gas is sent out of a boundary area under the pressure of about 0.02MPa (G), the adsorption temperature is controlled to be 15-40 ℃, the adsorption pressure is controlled to be 0.5-0.7MPa, the produced hydrogen with the purity of more than or equal to 85 percent is produced, the total effective components of the hydrogen in the discharged waste gas are less than or equal to 10 percent, and the yield of the hydrogen in the decarburization unit exceeds 99.0 percent.
3) Separation and purification: separation of H from waste gas by adsorption bed2And CO2、CO、CH4、N2And the components are equal, and the adsorbent in the adsorbent bed is filled according to the mass ratio: 4-5% of activated alumina at the lowest layer, 12-15% of activated carbon at the middle layer and 80-84% of molecular sieve at the upper layer; the hydrogen production adopts a single-bed adsorption procedure, namely a 6-1-3/P flow: the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and flushing regeneration processes. In the pressure swing adsorption system, 1 adsorption tower is always in the adsorption step at any moment, pressurized decarbonization gas is introduced from an inlet end, adsorption penetrating gas, namely product hydrogen, is output from an outlet end, and the rest adsorption towers are in different regeneration stages. Each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), forward pressure relief (PP), reverse pressure relief (D), flushing (P), 3 rd stage pressure equalization increase (E3R), 2 nd stage pressure equalization increase (E2R), 1 st stage pressure equalization increase (E1R), final pressure increase (FR) and the like. Each adsorption tower is operated circularly and alternately according to a set time sequence, adsorption penetrating gas is continuously output from the top of the adsorption tower and is sent to a hydrogen buffer tank to be buffered as product gas under the pressure of 1.25MPa (G) and then is sent out of a boundary area. The stripping gas from the reverse-discharge and flushing steps is discharged from the bottom of the column and is conveyed out of the battery limit at a pressure of about 0.02MPa (G). The adsorption temperature is controlled to be 15-40 ℃, the adsorption pressure is controlled to be 1.1-1.3MPa, hydrogen with the purity of more than or equal to 99.8 percent is produced, the effective component of the total hydrogen of the discharged waste gas is less than or equal to 55 percent, and the yield of the hydrogen production unit exceeds 85.0 percent.
The specific standards of the adsorbent are as follows:
activated carbon:
(1) the model is as follows: TN-15C
(2) Specification: phi 1.5-2 x 4mm
(3) The main physical and chemical properties are as follows: meets the standard GB7702-2008 and meets the following requirements
The gas static equilibrium adsorption capacity is realized under the conditions that the adsorption temperature is 25 ℃ and the adsorption pressure is 0.1MPa (absolute pressure).
Molecular sieve:
(1) model TN-5A
(2) The specification of phi 2-phi 3mm
(3) The main physical and chemical properties are as follows: meets the standard GB13550 and meets the following requirements
Silica gel:
(1) model TN-Si
(2) The specification of phi 2-phi 4mm
(3) The main physical and chemical properties are as follows: meets the standard HG/T2765-2005 and meets the following requirements
Gas static equilibrium adsorption capacity at an adsorption temperature of 25 ℃ and an adsorption pressure of 0.1MPa (absolute).
Claims (5)
1. A method for recovering and extracting hydrogen based on discharged flare waste gas is characterized in that: the method comprises the following specific steps:
1) and (3) transformation: performing conversion treatment on the waste gas by using a sulfur-tolerant cobalt rod-shift catalyst, wherein the content of CO in the recovered waste gas is calculated according to 30 percent, the proportion of steam to the waste gas is controlled to be 0.30-0.40, the steam and the waste gas are mixed in a mixing tank and then enter a conversion bed for conversion reaction, the inlet temperature of the conversion bed is controlled to be 220 ℃ and the bed reaction temperature is controlled to be 450 ℃ respectively, and CO is converted into hydrogen through the conversion reaction;
2) decarbonization: the waste gas after the conversion enters an adsorption bed for decarburization, and most of ineffective components CO in the gas after the conversion are removed2And N2High-pressure adsorption and low-pressure desorption; the adsorption bed adopts a single-bed adsorption process, and the adsorbent adopts activated alumina and silica gel;
3) separation and purification: for H in the waste gas after decarburization2And CO2、CO、CH4、N2Separating by adopting a single-bed adsorption procedure, and filling adsorbents of activated alumina, activated carbon and molecular sieve in the adsorption bed.
2. The method for recovering and extracting hydrogen based on the discharged flare waste gas as claimed in claim 1, wherein the method comprises the following steps: step 2) the adsorbent in the adsorbent bed is filled according to the mass ratio: 4-6% of lower active alumina and 94-96% of upper silica gel.
3. The method for recovering and extracting hydrogen based on the discharged flare waste gas as claimed in claim 1, wherein the method comprises the following steps: step 3) the adsorbent in the adsorbent bed is filled according to the mass ratio: 4-5% of activated alumina at the lowest layer, 12-15% of activated carbon at the middle layer and 80-84% of molecular sieve at the upper layer.
4. The method for recovering and extracting hydrogen based on the discharged flare waste gas as claimed in claim 1, wherein the method comprises the following steps: the single-bed adsorption process in the step 2) comprises the following steps: 6-1-3/V flow: the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and evacuation regeneration processes; each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), reverse pressure relief (D), evacuation (V), 3 rd stage pressure equalization rise (E3R), 2 nd stage pressure equalization rise (E2R), 1 st stage pressure equalization rise (E1R) and final pressure rise (FR); each adsorption tower is operated circularly and alternately according to a set time sequence, and adsorption penetrating gas is continuously output from the top of the adsorption tower; the desorption gas in the reverse discharging and evacuating steps is discharged from the bottom of the tower and is sent out of the battery limit zone under the pressure of about 0.02MPa (G), the adsorption temperature is controlled to be 15-40 ℃, and the adsorption pressure is controlled to be 0.5-0.7 MPa.
5. The method for recovering and extracting hydrogen based on the discharged flare waste gas as claimed in claim 1, wherein the method comprises the following steps: the single-bed adsorption procedure in the step 3) is a 6-1-3/P process; the system consists of 6 towers, 1 tower feeding, 3 times of pressure equalizing and flushing regeneration processes. In the pressure swing adsorption system, 1 adsorption tower is always in the adsorption step at any moment, pressurized decarbonization gas is introduced from an inlet end, adsorption penetrating gas (namely product hydrogen) is output from an outlet end, and the rest adsorption towers are in different regeneration stages; each adsorption column experiences, in sequence: adsorption (A), 1 st stage pressure equalization reduction (E1D), 2 nd stage pressure equalization reduction (E2D), 3 rd stage pressure equalization reduction (E3D), forward pressure relief (PP), reverse pressure relief (D), flushing (P), 3 rd stage pressure equalization increase (E3R), 2 nd stage pressure equalization increase (E2R), 1 st stage pressure equalization increase (E1R) and final pressure increase (FR); each adsorption tower is operated circularly and alternately according to a set time sequence, adsorption penetrating gas is continuously output from the top of the adsorption tower and is sent to a hydrogen buffer tank to be buffered as product gas under the pressure of 1.25MPa (G) and then is sent out of a boundary area. The stripping gas from the reverse-discharge and flushing steps is discharged from the bottom of the column and is conveyed out of the battery limit at a pressure of about 0.02MPa (G). The adsorption temperature is controlled at 15-40 deg.C, and the adsorption pressure is controlled at 1.1-1.3 MPa.
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| CN202111591463.6A CN114348962A (en) | 2021-12-23 | 2021-12-23 | Method for recovering and extracting hydrogen based on discharged torch waste gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111591463.6A CN114348962A (en) | 2021-12-23 | 2021-12-23 | Method for recovering and extracting hydrogen based on discharged torch waste gas |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0486174A1 (en) * | 1990-11-16 | 1992-05-20 | Texaco Development Corporation | Process for producing high purity hydrogen |
| CN102078740A (en) * | 2010-12-13 | 2011-06-01 | 甘肃银光聚银化工有限公司 | Method for separating and purifying hydrogen from water gas by pressure swing adsorption |
| CN102134056A (en) * | 2010-01-22 | 2011-07-27 | 上海寰球石油化学工程有限公司 | Combined process for preparing power generation co-production synthesis ammonia feed gas by using crude gas containing CH4 |
| CN111847381A (en) * | 2020-08-05 | 2020-10-30 | 昆明理工大学 | Method and device for preparing hydrogen from industrial waste gas |
-
2021
- 2021-12-23 CN CN202111591463.6A patent/CN114348962A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0486174A1 (en) * | 1990-11-16 | 1992-05-20 | Texaco Development Corporation | Process for producing high purity hydrogen |
| CN102134056A (en) * | 2010-01-22 | 2011-07-27 | 上海寰球石油化学工程有限公司 | Combined process for preparing power generation co-production synthesis ammonia feed gas by using crude gas containing CH4 |
| CN102078740A (en) * | 2010-12-13 | 2011-06-01 | 甘肃银光聚银化工有限公司 | Method for separating and purifying hydrogen from water gas by pressure swing adsorption |
| CN111847381A (en) * | 2020-08-05 | 2020-10-30 | 昆明理工大学 | Method and device for preparing hydrogen from industrial waste gas |
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Application publication date: 20220415 |