CN114031039A - Containing H2System and method for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production - Google Patents
Containing H2System and method for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000446 fuel Substances 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 88
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 58
- 229910052760 oxygen Inorganic materials 0.000 claims description 58
- 239000001301 oxygen Substances 0.000 claims description 58
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 30
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 18
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 17
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0447—Separation of the obtained sulfur
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a catalyst containing H2System and method for low-temperature chemical-looping desulfurization and co-production of sulfuric acid for S synthesis gas, wherein the system comprises a chemical-looping reaction unit, SO2To SO3Catalytic conversion unit, SO3An absorption acid making unit; the chemical chain reaction unit comprises an air reactor, a fuel reactor, a cyclone separator and a condenser; the SO2To SO3The catalytic conversion unit comprises a contact chamber; the SO3The absorption acid making unit comprises an absorption tower; the air reactor is connected with a cyclone separator through a riser, a lower discharge pipe of the cyclone separator is connected with the lower part of the fuel reactor, an airflow outlet of the cyclone separator is connected with an inlet of the contact chamber, an outlet of the contact chamber is connected with an inlet of the absorption tower through a pipeline, and the fuel reactsThe bottom of the reactor is connected with the air reactor through a material returning device, and the outlet of the fuel reactor is connected with a condenser. The invention realizes the resource utilization of sulfur while ensuring that the quality of the synthesis gas is not reduced.
Description
Technical Field
The invention belongs to the technical field of synthesis gas purification, and particularly relates to a method for purifying synthesis gasRelates to a catalyst containing H2A system and method for low-temperature chemical-looping desulfurization and co-production of sulfuric acid for S synthesis gas.
Background
Most primary energy sources contain elemental sulfur. The synthesis gas produced by energy conversion processes (e.g., gasification, reforming, fermentation, etc.) contains hydrogen sulfide (H) at a certain concentration2S) gas. H2S is a toxic gas with pungent odor, and has significant harm to equipment, human bodies and the environment. To prevent H2S gas affects equipment, products and the like in the process of deep energy conversion and resource utilization of synthesis gas, and the synthesis gas firstly needs to react with H2And removing the S gas. Under the premise of not influencing the quality of the synthesis gas, the H is added2Oxidation of S to sulfur dioxide (SO)2) SO produced2The deep conversion into sulfuric acid is one of the technical choices for resource utilization.
At present, H of industrial process2The technical route for preparing sulfuric acid from S mainly comprises the following steps: h2Oxidation of S and air, SO2To SO3Catalytic conversion and subsequent SO3Absorbing the acid making process. SO (SO)2To SO3Catalytic conversion and subsequent SO3The process of absorbing and preparing acid is relatively mature. H for the first step2S oxidation process, the traditional technique mostly adopts air as an oxidation medium, H2S and oxygen in the air are combusted in the combustion furnace to generate SO2. In the combustion furnace, when H2When the concentration of S is low, the S needs to be supported by combustible gas, namely H2S the combustion process provides a heat source. The temperature in the combustion furnace reaches thousands of degrees in the traditional process, H2S is contacted with oxygen and is easy to explode; meanwhile, the combustion supporting of the combustible gas consumes the high-quality combustible gas, which causes the waste of energy.
Construction of novel H-containing2The system and the method for low-temperature chemical-looping desulfurization and sulfuric acid co-production of S synthesis gas realize desulfurization of synthesis gas at low temperature and recycling of sulfur, and have wide social benefits and industrial prospects.
Disclosure of Invention
The technical problem is as follows: in order to overcome the conventional H2S-process for preparing sulfuric acidThe problem of waste of high temperature and combustible gas resources is solved by how to realize resource utilization of sulfur while ensuring that the quality of synthesis gas is not reduced.
The technical scheme is as follows: the invention provides a catalyst containing H2S synthetic gas low-temperature chemical-looping desulfurization and sulfuric acid co-production system and method.
Containing H of the invention2The system for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production comprises a chemical-looping reaction unit, SO2To SO3Catalytic conversion unit, SO3An absorption acid making unit; the chemical chain reaction unit comprises an air reactor, a fuel reactor, a cyclone separator and a condenser; the SO2To SO3The catalytic conversion unit comprises a contact chamber; the SO3The absorption acid making unit comprises an absorption tower; the air reactor is connected with the cyclone separator through a lifting pipe, a lower discharging pipe of the cyclone separator is connected with the lower part of the fuel reactor, an airflow outlet of the cyclone separator is connected with an inlet of the contact chamber, an outlet of the contact chamber is connected with an inlet of the absorption tower through a pipeline, the bottom of the fuel reactor is connected with the air reactor through a material returning device, and an outlet of the fuel reactor is connected with a condenser.
Further, an air reactor air distribution plate is arranged at the inlet of the air reactor, a fuel reactor air distribution plate is arranged at the bottom of the fuel reactor, and the air reactor air distribution plate and the fuel reactor air distribution plate are air distribution partition plates with porous shapes or hood structures.
Further, the catalyst within the contacting chamber may be arranged in two or more layers.
Further, the fuel reactor is a bubbling fluidized bed.
Further, an air inlet is provided at one side of the contact chamber.
With the above-mentioned hydrogen-containing compounds2System for low-temperature chemical-looping desulfurization and sulfuric acid co-production of S synthetic gas to contain H2The method for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production comprises the following steps:
(1) containing H2S synthetic gas enters the bottom of the fuel reactor, and H is generated under the action of an oxygen carrier2S gas is oxidized into elemental sulfur by an oxygen carrier, part of the generated elemental sulfur is attached to the surface of the oxygen carrier in a liquid phase form, the other part of the generated elemental sulfur and synthesis gas are discharged out of a fuel reactor in a gas phase form, the elemental sulfur is recycled after being condensed by a condenser, and the synthesis gas is purified; meanwhile, the oxygen carrier is reduced to a low valence state substance;
(2) preparation of SO by oxidation2Reaction: the sulfur simple substance attached to the surface of the oxygen carrier circulates to the air reactor along with the oxygen carrier to be combusted, and the oxygen carrier and the sulfur are subjected to oxidation reaction to generate SO under the air atmosphere2(ii) a Meanwhile, the reduced oxygen carrier from the fuel reactor enters the air reactor through the material returning device to perform oxidation reaction with the air entering from the bottom, so that the regeneration of the oxygen carrier is realized. The oxygen carrier after oxidation regeneration enters a cyclone separator through a riser, and the separated flue gas contains SO2The oxygen-depleted flue gas;
（3）SO2catalytic conversion reaction: containing SO2The oxygen-poor flue gas enters SO2To SO3Catalytic conversion unit, SO under the action of catalyst2Conversion to SO3；
(4) Absorption acid-making reaction: generated SO3Is absorbed into sulfuric acid in the absorption tower, thereby realizing resource conversion of sulfur.
Further, the synthesis gas comprises CO and H2、CH4One or a combination of two or more of them.
Further, the reaction temperature in the air reactor is 150-300 ℃; the reaction temperature in the fuel reactor is 150-300 ℃.
Has the advantages that:
1. the system and the method are suitable for the H-containing2S synthesis gas purification and resource utilization of sulfur are realized. Containing H2S synthetic gas is oxidized into elemental sulfur by an oxygen carrier in a fuel reactor, partial elemental sulfur can be directly recycled, and sulfur loaded on the oxygen carrier in a liquid phase enters an air reactor to be oxidized into SO2SO formed2Entering a subsequent acid making system and being used for H2SO4And (4) preparation.
2. The fuel reactor has low operation temperature of 150-300 ℃ and oxygen carrier capable of oxidizing H only2S is elemental sulfur, the synthesis gas does not react with the oxygen carrier, and the quality of the synthesis gas is not influenced by materials and operating conditions in the fuel reactor. The sulfur resource is recycled and the function of purifying the synthesis gas is achieved.
Drawings
FIG. 1 is a schematic diagram of a chemical looping low temperature oxidation process;
FIG. 2 is a system flow diagram of the present invention;
FIG. 3 is a system block diagram of the present invention;
FIG. 4 is a diagram of an experimental system constructed according to a specific embodiment;
fig. 5 is a diagram showing sulfur recycling efficiency of the embodiment, and in fig. 5, (a) shows temperature and sulfur recycling efficiency, and (b) shows gas concentration and sulfur recycling efficiency.
The reference numerals in the figures represent the following:
1. a chemical-looping reactor unit; 2. SO (SO)2To SO3A catalytic conversion unit; 3. SO (SO)3And absorbing an acid making unit.
1-1. an air reactor; 1-2, a riser; 1-3. a cyclone separator; 1-4. a fuel reactor; 1-5, a material returning device; 1-6. air distribution plate of air reactor; 1-7, a discharge pipe; 1-8. air distribution plate of fuel reactor; 1-9. fuel reactor gas inlet; 1-10. air reactor gas inlet; 1-11. an airflow outlet of the cyclone separator; 1-12. fuel reactor outlet; 1-13. a condenser; 1-14. condenser outlet; 1-15, connecting the pipeline.
2-1. a contacting chamber; 2-2. contacting chamber inlet; 2-3. an air inlet; 2-4. a contact chamber outlet; 2-5, connecting the pipeline.
3-1, an absorption tower; 3-2, an absorption tower inlet; 3-3, a liquid outlet of the absorption tower; and 3-4, a tail gas outlet of the absorption tower.
4-1, a mass flow meter; 4-2, valve one; 4-3, thermocouple; 4-4. a condenser; 4-5, valve II; 4-6.H2S, an analyzer; 4-7. SO2An analyzer; 4-8, PC end.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
Example 1
The invention relates to a catalyst containing H2The system for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production is shown in figure 2 and comprises a chemical-looping reactor unit 1, SO2To SO3Catalytic conversion unit 2 and SO3An absorption acid-making unit 3.
Further, as shown in FIG. 3, the chemical looping reaction unit 1 is a circulating bed material device composed of an air reactor 1-1, a riser 1-2, a cyclone separator 1-3, a fuel reactor 1-4 and a return feeder 1-5. The upper part of the air reactor 1-1 is communicated with a cyclone separator 1-3 through a riser 1-2; the J-shaped discharge pipe 1-7 at the lower part of the cyclone separator 1-3 is introduced into the lower part of the fuel reactor 1-4; the fuel reactor 1-4 is communicated with the air reactor 1-1 through a return feeder 1-5. The air distribution plate 1-6 of the air reactor is arranged at the inlet 1-10 of the air reactor, the air distribution plate 1-8 of the fuel reactor is arranged at the bottom 1-9 of the fuel reactor, and the air distribution plate 1-6 of the air reactor and the air distribution plate 1-8 of the fuel reactor are air distribution partition plates with porous shapes or air cap structures and are used for supporting bed materials.
The synthesis gas at the fuel reactor outlet 1-12 enters the condenser 1-13 and is discharged through the condenser outlet 1-14. An airflow outlet 1-11 of the cyclone separator is connected with an inlet 2-2 of the contact chamber through a connecting pipeline 1-15; the air reactor stream enters the contactor 2-1 from contactor inlet 2-2; SO (SO)2To SO3The air inlet 2-3 in the catalytic conversion unit 2 is used for assisting SO2To SO3A supplemental air inlet for catalytic conversion.
SO2To SO3The outlet 2-4 of the contact chamber of the catalytic conversion unit 2 is connected with the inlet 3-2 of the absorption tower through a connecting pipeline 2-5; the gas flow after catalytic conversion enters an absorption tower 3-1 from an inlet 3-2 of the absorption tower; the sulfuric acid liquid is discharged through a liquid outlet 3-3 of the absorption tower, and the tail gas is discharged through a tail gas outlet 3-4 of the absorption tower.
The catalyst in the contacting chamber in this embodiment may be arranged in two or more layers.
With the above-mentioned hydrogen-containing compounds2S syngas cryochemistrySystem for carrying out chain desulfurization and co-production of sulfuric acid to contain H2Method for low-temperature chemical-looping desulfurization and co-production of sulfuric acid from S synthesis gas containing H2The synthesis gas of S enters a fuel reactor, and the function of purifying the synthesis gas is realized while the resource of sulfur is changed by the circulation of the circulating oxygen carrier in the device, and the specific method comprises the following steps:
and (3) synthetic gas purification reaction: the fuel reactor is a bubbling fluidized bed and contains H2S synthetic gas enters the bottom of the fuel reactor, and H is generated under the action of an oxygen carrier2S gas is oxidized into elemental sulfur by an oxygen carrier, part of the generated elemental sulfur is attached to the surface of the oxygen carrier in a liquid phase form, the other part of the generated elemental sulfur and synthesis gas are discharged out of a fuel reactor in a gas phase form, the elemental sulfur can be recycled after condensation by a condenser, and the synthesis gas is purified; at the same time, the oxygen carrier is reduced to a lower valence state.
Preparation of SO by oxidation2Reaction: the sulfur simple substance attached to the surface of the oxygen carrier circulates to the air reactor along with the oxygen carrier to be combusted, and the oxygen carrier and the sulfur are subjected to oxidation reaction to generate SO under the air atmosphere2. Meanwhile, the reduced oxygen carrier from the fuel reactor enters the air reactor through the material returning device to perform oxidation reaction with the air entering from the bottom, so that the regeneration of the oxygen carrier is realized. The oxygen carrier after oxidation regeneration enters a cyclone separator through a riser, and the separated flue gas contains SO2Is used to remove the oxygen-depleted flue gas.
SO2Catalytic conversion reaction: containing SO2The oxygen-poor flue gas enters SO2To SO3Catalytic conversion unit, SO under the action of catalyst2Conversion to SO3。
Absorption acid-making reaction: generated SO3Is absorbed into sulfuric acid in the absorption tower, thereby realizing resource conversion of sulfur.
The synthesis gas in the embodiment is CO and H2、CH4And the like.
H in the present example2The S inlet concentration range is as follows: 0 to Vol.100 percent.
The oxygen carrier described in this embodiment is: can be combined with H2All oxygen carriers for the oxidation of S to elemental sulfur, the composition of which comprisesActive substance and inert carrier. For example: v2O5/TiO2An oxygen carrier.
In the embodiment, the reaction temperature in the air reactor is 150-300 ℃; the reaction temperature in the fuel reactor is 150-300 ℃.
In this embodiment, the fluidizing gas at the bottom of the air reactor is: air; the fuel reactor adds reaction gas through the bottom: a synthesis gas comprising hydrogen sulphide.
Example 2
The experimental system is built in the embodiment, and the system can simulate a real low-temperature chemical chain process through switching of air flows. As shown in fig. 4, the system mainly comprises a gas input, a reactor, a condenser and an on-line analysis of the gas. The reactor adopts a miniature vertical tube furnace, and a furnace tube with the inner diameter of 25mm is adopted in the furnace and is made of quartz; the furnace tube is arranged in an electric heating furnace, and the heating power is 3 kW; the outlet of the reactor is provided with a condenser for condensing the flue gas at the outlet of the reactor and part of elemental sulfur; a gas bypass is arranged between the outlet of the reactor and the analyzer to ensure that gas with stable concentration enters the reactor to participate in reaction. The gas analyzer adopts ultraviolet and infrared principles to carry out on-line detection on gas at the outlet of the reactor.
The main operating procedures in the experiment are as follows
Step S1: connecting the pipeline with gas H2S、N2And O2In which N is2As a carrier gas; h2S and N2As gas in the reduction process, O2And N2The mixed gas is used as the gas of the oxidation process; checking the air tightness and ensuring that each device is in a normal working state.
Step S2: opening H2S gas and SO2And the gas analyzer is connected with a computer, and data are exported in real time.
Step S3: arranging an oxygen carrier bed material in a furnace; the oxygen carrier in this example is V2O5/TiO2An oxygen carrier.
Step S4: the tube furnace switch was turned on, the temperature programmed and run was started, the example temperature was 150 ℃ 200 ℃ and 250 ℃; inlet H2The S concentrations were 1000ppm, 2000ppm and 4000 ppm.
Step S5: when the temperature reaches and stabilizes at the target temperature, a concentration of H2S and N2Introducing the mixed gas into a reactor, wherein the reaction time is 2 minutes; then, H is stopped2S is introduced, N is adopted2Purging the reactor for 4 minutes; finally, O is introduced2And N2The time of the mixed gas is 2 minutes.
Step S6: the experiment is repeated for 20 times under the same batch of oxygen carrier bed materials under the above experimental working conditions. And after the experiment is finished, stopping heating the furnace body, closing the gas mass flow controller after the temperature is reduced to the room temperature, and sequentially closing the tube furnace and the analyzer.
Step S7: and (4) closing the gas cylinder, and emptying residual gas in the gas circuit to reduce the indication value of the pressure reducing valve to 0.
The synthesis gas containing hydrogen sulfide passes through a bed layer formed by oxygen carrier particles in a reactor; wherein, the hydrogen sulfide is oxidized by the oxygen carrier to generate sulfur simple substance, and the oxygen carrier is reduced to suboxide; according to the experimental result, as shown in fig. 5, most elemental sulfur adheres to the surface of the oxygen carrier, and only a small amount of elemental sulfur is carried by the gas and enters the condenser to be collected; in the air oxidation process, the reduced oxygen carrier reacts with oxygen in the air to realize the regeneration of the oxygen carrier; simultaneously, the sulfur simple substance on the surface of the oxygen carrier reacts with the oxidized oxygen carrier to generate a large amount of SO2The part of SO2Can be used for accessing subsequent SO2In a catalytic conversion system.
Gas analyzer real-time recording H per second2S and SO2Concentration values, for the examples, define H2S conversion and SO2The production rate was as follows:
as shown in fig. 5, it can be found that: even at a reaction temperature of 150 ℃ H2When S inlet gas concentration is 2000ppm, more than 82% of H still exists2S is converted into elemental sulfur; at the same time, SO2The yield was about 70%. When gas H2SO when the concentration of S is 1000ppm2The yield can reach 82%. Compared with the traditional sulfuric acid preparation process route, the temperature of over 1000 ℃ is required to generate SO2The invention greatly saves the cost.
In the embodiment, the formula of the oxygen carrier and the filling ratio of the oxygen carrier are optimized, so that the H content is still greatly improved2S conversion and SO2Space of generation rate.
The above examples are only preferred embodiments of the present invention, it should be noted that: the invention can be applied to various fields of medical equipment, such as medical equipment, etc. without departing from the principle of the invention.
Claims (8)
1. Containing H2The system for low-temperature chemical-looping desulfurization and co-production of sulfuric acid of S synthesis gas is characterized by comprising a chemical-looping reaction unit (1), SO2To SO3Catalytic conversion unit (2), SO3An absorption acid-making unit (3); the chemical chain reaction unit (1) comprises an air reactor (1-1), a fuel reactor (1-4), a cyclone separator (1-3) and a condenser (1-13); the SO2To SO3The catalytic conversion unit (2) comprises a contact chamber (2-1); the SO3The absorption acid making unit (3) comprises an absorption tower (3-1); the air reactor (1-1) is connected with the cyclone separator (1-3) through a lifting pipe (1-2), a lower discharging pipe 1-7 of the cyclone separator (1-3) is connected with the lower part of the fuel reactor (1-4), an airflow outlet (1-11) of the cyclone separator (1-3) is connected with an inlet (2-2) of the contact chamber, an outlet (2-4) of the contact chamber is connected with an inlet (3-2) of the absorption tower through a pipeline, the bottom of the fuel reactor (1-4) is connected with the air reactor (1-1) through a material returning device (1-5), and the fuel is reversely fed into the air reactor (1-1)The outlet (1-12) of the reactor is connected with a condenser (1-13).
2. The H-containing according to claim 12The system for low-temperature chemical-looping desulfurization and sulfuric acid coproduction of synthesis gas is characterized in that an air reactor air distribution plate (1-6) is arranged at an inlet of an air reactor (1-1), a fuel reactor air distribution plate (1-8) is arranged at the bottom of a fuel reactor (1-4), and the air reactor air distribution plate (1-6) and the fuel reactor air distribution plate (1-8) are air distribution partition plates with porous shapes or hood structures.
3. The H-containing according to claim 12The system for low-temperature chemical-looping desulfurization and sulfuric acid coproduction of the S synthesis gas is characterized in that catalysts in the contact chamber (2-1) are arranged in two or more layers.
4. The H-containing according to claim 12The system for low-temperature chemical-looping desulfurization and sulfuric acid co-production of the S synthesis gas is characterized in that the fuel reactor (1-4) is a bubbling fluidized bed.
5. The H-containing according to claim 12The system for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid coproduction is characterized in that an air inlet (2-3) is formed in one side of the contact chamber (2-1).
6. By using the above-mentioned hydrogen-containing material2System for low-temperature chemical-looping desulfurization and sulfuric acid co-production of S synthetic gas to contain H2The method for S synthesis gas low-temperature chemical-looping desulfurization and sulfuric acid co-production comprises the following steps:
(1) containing H2S synthetic gas enters the bottom of the fuel reactor (1-4), and under the action of an oxygen carrier, H2S gas is oxidized into elemental sulfur by an oxygen carrier, part of the generated elemental sulfur is attached to the surface of the oxygen carrier in a liquid phase form, the other part of the generated elemental sulfur and the synthesis gas are discharged from a fuel reactor in a gas phase form, the elemental sulfur is recycled after the condensation by a condenser (1-13), and the synthesis gas is purified;meanwhile, the oxygen carrier is reduced to a low valence state substance;
(2) preparation of SO by oxidation2Reaction: the sulfur simple substance attached to the surface of the oxygen carrier circulates to the air reactor (1-1) along with the oxygen carrier to be combusted, and the oxygen carrier and the sulfur are subjected to oxidation reaction to generate SO under the air atmosphere2(ii) a Meanwhile, reduced oxygen carrier from the fuel reactor (1-4) enters the air reactor (1-1) through a material returning device to perform oxidation reaction with air entering from the bottom, SO that the regeneration of the oxygen carrier is realized, the oxygen carrier after oxidation regeneration enters the cyclone separator (1-3) through the lifting pipe (1-2), and the separated flue gas contains SO2The oxygen-depleted flue gas;
（3）SO2catalytic conversion reaction: containing SO2The oxygen-poor flue gas enters SO2To SO3A catalytic conversion unit (2) for SO under the action of a catalyst2Conversion to SO3；
(4) Absorption acid-making reaction: generated SO3Is absorbed into sulfuric acid in the absorption tower (3-1) to realize resource conversion of sulfur.
7. The method of claim 6, wherein the syngas comprises CO, H2、CH4One or a combination of two or more of them.
8. The method according to claim 6, wherein the reaction temperature in the air reactor (1-1) is 150 to 300 ℃; the reaction temperature in the fuel reactor (1-4) is 150-300 ℃.
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| CN115974082A (en) * | 2023-02-23 | 2023-04-18 | 会东金川磷化工有限责任公司 | Device for preparing calcium carbide by recycling yellow phosphorus tail gas |
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