CN108516524B - Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide - Google Patents
Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide Download PDFInfo
- Publication number
- CN108516524B CN108516524B CN201810168167.7A CN201810168167A CN108516524B CN 108516524 B CN108516524 B CN 108516524B CN 201810168167 A CN201810168167 A CN 201810168167A CN 108516524 B CN108516524 B CN 108516524B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sulfur
- reduction reaction
- wall
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 238
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000011593 sulfur Substances 0.000 title claims abstract description 83
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 154
- 239000007789 gas Substances 0.000 claims abstract description 142
- 238000006722 reduction reaction Methods 0.000 claims abstract description 76
- 239000003546 flue gas Substances 0.000 claims abstract description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 113
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000004291 sulphur dioxide Substances 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDHOKIPTZNSSEK-UHFFFAOYSA-N O=C=O.O=S=O Chemical compound O=C=O.O=S=O XDHOKIPTZNSSEK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
-
- 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
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a cross-flow moving device and a method for continuously preparing sulfur by sulfur dioxide. The cross-flow moving device comprises: the reduction reaction chamber is provided with a sulfur dioxide-containing flue gas inlet, a reduction gas inlet, a catalyst inlet, a sulfur-containing gas outlet and a catalyst outlet, the sulfur dioxide-containing flue gas inlet, the reduction gas inlet and the sulfur-containing gas outlet are positioned on the side wall of the reduction reaction chamber, the catalyst inlet is positioned on the top wall of the reduction reaction chamber, and the catalyst outlet is positioned on the bottom wall of the reduction reaction chamber; a catalyst supply unit connected to the catalyst inlet to supply a catalyst to the reduction reaction chamber; the catalyst collecting unit is connected with the catalyst outlet; and the sulfur collecting unit is connected with the sulfur-containing gas outlet. By adopting the cross-flow moving device, the aim of reducing sulfur dioxide into sulfur is fulfilled with lower energy consumption, the reduction reaction is continuously carried out, the sulfur product is continuously separated, and the industrial implementation is easy.
Description
Technical Field
The invention relates to the field of sulfur dioxide treatment, in particular to a cross-flow moving device and a method for continuously preparing sulfur from sulfur dioxide.
Background
The combustion of coal, natural gas, petroleum, biomass, etc. produces a large amount of SO2The direct emission of the flue gas can cause pollution and damage to the environment. Currently, SO is industrially controlled2The pollutant discharge technology is more, such as limestone-gypsum wet desulphurization technology, ammonia desulphurization technology, calcium-based dry/semi-dry desulphurization technology, activated coke adsorption desulphurization technology, ionic liquid absorption desulphurization technology and the like. Wherein, the active coke adsorption desulfurization technology and the ionic liquid absorption desulfurization technology can recover SO in the flue gas2The Claus process is adopted to realize resource utilization, and the resource-utilized finished product mainly contains sulfuric acid and can provide raw materials required by production for the steel and metallurgy industries.
However, the resource products limit the application and development of the active coke adsorption desulfurization technology and the ionic liquid absorption desulfurization technology in other industries such as power production. The direct reduction (reducing agent including H) is formed because of the easy storage and transportation of elemental sulfur2、CH4CO, activated carbon, etc.) to remove SO2The technology for preparing the elemental sulfur by reduction is relatively immature compared with the process for preparing the sulfuric acid by Claus, so the technology is mainly focused on laboratory research, and industrial devices and processes suitable for large-scale production are rare.
Disclosure of Invention
The invention mainly aims to provide a cross-flow moving device and a cross-flow moving method for continuously preparing sulfur by sulfur dioxide, so as to solve the problem that the industrial preparation of the sulfur by the sulfur dioxide is difficult to realize in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a cross-flow moving apparatus for continuously producing sulfur from sulfur dioxide, the cross-flow moving apparatus comprising: the reduction reaction chamber is provided with a sulfur dioxide-containing flue gas inlet, a reduction gas inlet, a catalyst inlet, a sulfur-containing gas outlet and a catalyst outlet, the sulfur dioxide-containing flue gas inlet, the reduction gas inlet and the sulfur-containing gas outlet are positioned on the side wall of the reduction reaction chamber, the catalyst inlet is positioned on the top wall of the reduction reaction chamber, and the catalyst outlet is positioned on the bottom wall of the reduction reaction chamber; a catalyst supply unit connected to the catalyst inlet to supply a catalyst to the reduction reaction chamber; the catalyst collecting unit is connected with the catalyst outlet; and the sulfur collecting unit is connected with the sulfur-containing gas outlet.
Further, the side wall of the reduction reaction chamber includes: the gradually expanding wall is provided with a sulfur dioxide-containing flue gas inlet and a reducing gas inlet at the initial end; the reducing wall is arranged opposite to the gradually expanding wall, and the sulfur-containing gas outlet is arranged at the tail end of the reducing wall; and a main sidewall connected between the tapered wall and the diverging wall.
Further, the reduction reaction chamber is provided with: the first gas distributor is fixedly arranged at the joint of the gradually expanding wall and the main side wall; the second gas distributor is fixedly arranged at the joint of the tapered wall and the main side wall; and a reaction zone disposed between the first gas distributor and the second gas distributor.
Further, the above catalyst collection unit includes: the catalyst collecting tank is arranged below the reduction reaction chamber, and the wall of the catalyst collecting tank is connected with the side wall of the reduction reaction chamber; the first heat exchanger is connected and arranged below the catalyst collecting tank; and the catalyst switch valve is arranged on a pipeline between the catalyst collecting tank and the heat exchanger.
Further, the sulfur collecting unit includes: the second heat exchanger is connected with the sulfur-containing gas outlet; and the sulfur collector is arranged at the downstream of the second heat exchanger and is connected with the sulfur-containing gas outlet through the second heat exchanger.
Further, the catalyst supply unit includes: and the catalyst storage bin is arranged above the reduction reaction chamber, and a catalyst discharging valve is arranged on a connecting pipeline between the catalyst storage bin and the catalyst inlet.
According to another aspect of the present invention, there is provided a process for continuously producing sulfur from sulfur dioxide, the process comprising: the sulfur-containing gas is obtained by carrying out catalytic reduction reaction on the sulfur dioxide-containing flue gas and the reducing gas in a mode of cross-flow contact with a catalyst, and the sulfur-containing gas is continuously separated from the catalyst while the catalytic reduction reaction is carried out, so that sulfur is obtained.
Further, the above catalytic reduction reaction is performed in a reduction reaction chamber, a side wall of which includes: the starting end of the gradually expanding wall is provided with a sulfur dioxide-containing flue gas inlet and a reducing gas inlet; the reducing wall is arranged opposite to the gradually expanding wall, and the tail end of the reducing wall is provided with a sulfur-containing gas outlet; and a main sidewall connected between the tapered wall and the diverging wall.
Further, the reduction reaction chamber is provided with: the first gas distributor is arranged at the joint of the gradually expanding wall and the main side wall; the second gas distributor is arranged at the joint of the tapered wall and the main side wall; and a reaction zone disposed between the first gas distributor and the second gas distributor, wherein a catalytic reduction reaction occurs in the reaction zone.
Further, the catalyst is selected from any one of activated carbon and activated coke, and preferably, the reducing gas is H2、CH4And CO.
Further, the moving speed of the catalyst is 0.05 m/h-1 m/s, the residence time of the sulfur dioxide-containing flue gas in the reaction zone is preferably 4-15 s, the thickness of the catalyst is preferably 0.5-3 m along the flowing direction of the sulfur dioxide-containing flue gas, and the catalyst enters and/or flows out of the reduction reaction chamber under the protection of nitrogen or inert gas.
Further, the reaction temperature of the catalytic reduction reaction is 200-800 ℃, and the flow resistance of the flue gas containing sulfur dioxide in the reaction zone is controlled to be 200-2000 Pa.
Further, the sulfur-containing gas and the catalyst are cooled after being separated, and preferably, water, heat transfer oil or steam is used for cooling.
By applying the technical scheme of the invention, the catalyst inlet is arranged on the top wall of the reduction reaction chamber, so that the catalyst falls under the action of gravity; meanwhile, the sulfur dioxide-containing flue gas inlet and the reducing gas inlet are arranged on the side wall of the reduction reaction chamber, so that the airflow flows in the horizontal direction, the cross flow contact of the catalyst with the sulfur dioxide and the reducing gas is realized, the airflow resistance of the sulfur dioxide and the reducing gas is reduced, and the purposes of reaction and separation are realized on the basis of ensuring the contact time of the catalyst with the sulfur dioxide and the reducing gas. Therefore, the cross-flow moving device not only achieves the aim of reducing sulfur dioxide into sulfur with low energy consumption, but also achieves continuous reduction reaction and continuous separation of sulfur products, and is easy for industrial implementation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of a cross-flow moving device provided in accordance with a preferred embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a reduction reaction chamber; 11. a gradually expanding wall; 12. a tapered wall; 13. a main side wall; 14. a first gas distributor; 15. a second gas distributor; 16. a reaction zone;
01. a flue gas inlet containing sulfur dioxide; 02. a reducing gas inlet; 03. a catalyst inlet; 04. an outlet for sulfur-containing gas; 05. a catalyst outlet;
20. a catalyst supply unit; 21. a catalyst storage bin; 22. a catalyst discharge valve;
30. a catalyst collection unit; 31. a catalyst collection tank; 32. a first heat exchanger; 33. a catalyst on-off valve;
40. a sulfur collection unit; 41. a second heat exchanger; 42. a sulfur collector.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background of the present application, SO is now being incorporated2The technology for preparing the elemental sulfur by reduction is mainly concentrated in a laboratory, and industrial devices suitable for large-scale production are rare, so that the elemental sulfur is difficult to prepareSo as to realize the industrial preparation of sulfur by sulfur dioxide. In order to solve the problem, the application provides a cross-flow moving device and a method for continuously preparing sulfur by sulfur dioxide.
In an exemplary embodiment of the present application, a cross-flow moving device for continuously producing sulfur from sulfur dioxide is provided, as shown in fig. 1, the cross-flow moving device includes a reduction reaction chamber 10, a catalyst supply unit 20, a catalyst collection unit 30, and a sulfur collection unit 40, the reduction reaction chamber 10 has a sulfur dioxide-containing flue gas inlet 01, a reduction gas inlet 02, a catalyst inlet 03, a sulfur-containing gas outlet 04, and a catalyst outlet 05, the sulfur dioxide-containing flue gas inlet 01, the reduction gas inlet 02, and the sulfur-containing gas outlet 04 are located on a side wall of the reduction reaction chamber 10, the catalyst inlet 03 is located on a top wall of the reduction reaction chamber 10, and the catalyst outlet 05 is located on a bottom wall of the reduction reaction chamber 10; the catalyst supply unit 20 is connected to the catalyst inlet 03 to supply a catalyst to the reduction reaction chamber 10; the catalyst collection unit 30 is connected to the catalyst outlet 05; the sulfur collecting unit 40 is connected with the sulfur-containing gas outlet 04.
The catalyst inlet 03 is arranged on the top wall of the reduction reaction chamber 10, so that the catalyst falls under the action of gravity; meanwhile, the sulfur dioxide-containing flue gas inlet 01 and the reducing gas inlet 02 are arranged on the side wall of the reduction reaction chamber 10, so that the airflow flows in the horizontal direction, the cross flow contact of the catalyst with the sulfur dioxide and the reducing gas is realized, the airflow resistance of the sulfur dioxide and the reducing gas is reduced, and the purposes of reaction and separation are realized on the basis of ensuring the contact time of the catalyst with the sulfur dioxide and the reducing gas. Therefore, the cross-flow moving device not only achieves the aim of reducing sulfur dioxide into sulfur with low energy consumption, but also achieves continuous reduction reaction and continuous separation of sulfur products, and is easy for industrial implementation.
In order to increase the contact area between the sulfur dioxide-containing flue gas and the reducing gas and the catalyst, it is preferable that, as shown in fig. 1, the side walls of the reduction reaction chamber 10 include a gradually expanding wall 11, a gradually reducing wall 12, and a main side wall 13, and the sulfur dioxide-containing flue gas inlet 01 and the reducing gas inlet 02 are provided at the beginning of the gradually expanding wall 11; the reducing wall 12 is arranged opposite to the diverging wall 11, and the sulfur-containing gas outlet 04 is arranged at the tail end of the reducing wall 12; the main side wall 13 is connected between the tapered wall 11 and the tapered wall 12. The flue gas containing sulfur dioxide and reducing gas enter the reduction reaction chamber 10 through a gradually-expanding channel formed by the gradually-expanding wall 11, so that the airflow resistance is reduced, and the airflow area is increased, thereby increasing the contact area with the catalyst and ensuring the full contact with the catalyst; the sulfur-containing gas generated after the reaction flows out of the reduction reaction chamber 10 through the tapered passage formed by the tapered wall 12, so that the gas flow resistance is increased and the gas flow area is reduced, thereby enabling the unreacted gas to have enough retention time to participate in the reaction.
In addition, in order to further enhance the uniformity of the gas participating in the reaction, it is preferable that as shown in fig. 1, a first gas distributor 14, a second gas distributor 15 and a reaction zone 16 are provided in the reduction reaction chamber 10, the first gas distributor 14 is fixedly provided at the junction of the divergent wall 11 and the main side wall 13; the second gas distributor 15 is fixedly arranged at the connection part of the tapered wall 12 and the main side wall 13; a reaction zone 16 is disposed between the first gas distributor 14 and the second gas distributor 15. The first gas distributor 14 is utilized to carry out gas uniform distribution on the flue gas containing sulfur dioxide and the reducing gas which participate in the reaction, so that the contact uniformity of the reaction gas and the catalyst is improved; the gas after reaction is distributed by the second gas distributor 15, so that the gas after reaction can be uniformly and intensively discharged, the turbulence degree of the gas flow is weakened, and the system resistance is reduced.
In one embodiment of the present application, in order to better control the flow rate of the catalyst, it is preferable that, as shown in fig. 1, the catalyst collection unit 30 includes a catalyst collection tank 31, a first heat exchanger 32, and a catalyst switching valve 33, the catalyst collection tank 31 is disposed below the reduction reaction chamber 10, and a wall of the catalyst collection tank 31 is connected to a side wall of the reduction reaction chamber 10; the first heat exchanger 32 is connected and arranged below the catalyst collecting tank 31; a catalyst on-off valve 33 is provided on the line between the catalyst collection tank 31 and the heat exchanger. The catalyst switch valve 33 is used for controlling the releasing speed of the catalyst after the catalytic reaction, so that the retention time of the catalyst in the reaction zone 16 is effectively controlled, and the application of the catalyst is more sufficient.
In order to better meet the industrialization requirement, preferably, as shown in fig. 1, the sulfur collection unit 40 comprises a second heat exchanger 41 and a sulfur collector 42, wherein the second heat exchanger 41 is connected with the sulfur-containing gas outlet 04; the sulfur collector 42 is arranged downstream of the second heat exchanger 41 and is connected with the sulfur-containing gas outlet 04 through the second heat exchanger 41. The separated gaseous sulfur is converted into liquid sulfur after heat exchange, and then enters the sulfur collector 42 for storage and transportation.
Further, as shown in fig. 1, it is preferable that the catalyst supply unit 20 includes a catalyst storage bin 21, the catalyst storage bin 21 is disposed above the reduction reaction chamber 10, and a catalyst discharge valve 22 is disposed on a connection line with the catalyst inlet 03. The catalyst residence time can also be controlled by adjusting the catalyst feed rate via the catalyst discharge valve 22, making the cross-flow moving device of the present application more flexible to use.
In another exemplary embodiment of the present application, there is provided a method for continuously producing sulfur from sulfur dioxide, the method comprising: the sulfur-containing gas is obtained by carrying out catalytic reduction reaction on the sulfur dioxide-containing flue gas and the reducing gas in a mode of cross-flow contact with a catalyst, and the sulfur-containing gas is continuously separated from the catalyst while the catalytic reduction reaction is carried out, so that sulfur is obtained.
The catalyst of the application falls under the action of gravity, and the airflow containing the sulfur dioxide flue gas inlet 01 and the airflow containing the reducing gas inlet 02 flows in the horizontal direction, so that the cross flow contact of the catalyst and sulfur dioxide and the reducing gas is realized, the airflow resistance of the sulfur dioxide and the reducing gas is reduced, and the purposes of reaction and separation are realized on the basis of ensuring the contact time of the catalyst and the sulfur dioxide and the reducing gas. Therefore, the method not only realizes the purpose of reducing sulfur dioxide into sulfur with lower energy consumption, but also realizes the continuous operation of the reduction reaction and the continuous separation of sulfur products, and is easy for industrial implementation.
In a preferred embodiment of the present application, the catalytic reduction reaction is performed in a reduction reaction chamber 10, as shown in fig. 1, the side wall of the reduction reaction chamber 10 comprises a gradually expanding wall 11, a gradually reducing wall 12 and a main side wall 13, and the beginning end of the gradually expanding wall 11 is provided with a sulfur dioxide-containing flue gas inlet 01 and a reducing gas inlet 02; the reducing wall 12 is arranged opposite to the gradually expanding wall 11, and the tail end of the reducing wall 12 is provided with a sulfur-containing gas outlet 04; the main side wall 13 is connected between the tapered wall 11 and the tapered wall 12. The flue gas containing sulfur dioxide and reducing gas enter the reduction reaction chamber 10 through a gradually-expanding channel formed by the gradually-expanding wall 11, so that the airflow resistance is reduced, and the airflow area is increased, thereby increasing the contact area with the catalyst and ensuring the full contact with the catalyst; the sulfur-containing gas generated after the reaction flows out of the reduction reaction chamber 10 through the tapered passage formed by the tapered wall 12, so that the gas flow resistance is increased and the gas flow area is reduced, thereby enabling the unreacted gas to have enough retention time to participate in the reaction.
Preferably, as shown in fig. 1, a first gas distributor 14, a second gas distributor 15 and a reaction zone 16 are arranged in the reduction reaction chamber 10, and the first gas distributor 14 is arranged at the connection part of the tapered wall 11 and the main side wall 13; a second gas distributor 15 is provided at the junction of the tapered wall 12 and the main side wall 13; a reaction zone 16 is disposed between the first gas distributor 14 and the second gas distributor 15, and a catalytic reduction reaction occurs in the reaction zone 16. The first gas distributor 14 is utilized to carry out gas uniform distribution on the flue gas containing sulfur dioxide and the reducing gas which participate in the reaction, so that the contact uniformity of the reaction gas and the catalyst is improved; the gas after reaction is distributed by the second gas distributor 15, so that the gas after reaction can be uniformly and intensively discharged, the turbulence degree of the gas flow is weakened, and the system resistance is reduced.
The catalyst and reducing gas used in the present application may refer to the catalyst and reducing gas used for catalyzing the conversion of sulfur dioxide into sulfur in the prior art, and in order to save cost, the catalyst is preferably selected from any one of activated carbon and activated coke, and the reducing gas is more preferably H2、CH4And CO.
In order to improve the catalytic efficiency of the catalyst, the moving speed of the catalyst is preferably between 0.05m/h and 1m/s, the residence time of the flue gas containing sulfur dioxide in the reaction zone 16 is preferably between 4 and 15s, preferably between 4 and 6s, and the catalyst enters and/or flows out of the reduction reaction chamber 10 under the protection of nitrogen or inert gas. Further, in order to prolong the contact time of the flue gas containing sulfur dioxide and the reducing gas with the catalyst as far as possible and ensure that the resistance is reduced as far as possible, the thickness of the catalyst is preferably between 0.5 and 3m, preferably between 0.5 and 1m, along the flow direction of the flue gas containing sulfur dioxide, so as to realize smaller system resistance.
The reaction temperature of the catalytic reduction reaction of this application can go on in current experimental temperature range, and the reaction based on this application is the serialization reaction, therefore the reaction heat can disperse relatively fast, therefore its reaction temperature can suitably increase for prior art, and the reaction temperature of preferred above-mentioned catalytic reduction reaction is between 200 ~ 800 ℃ in order to improve reaction efficiency. In addition, in order to reduce the industrial operation cost, the flow resistance of the flue gas containing sulfur dioxide in the reaction zone 16 is controlled to be 200-2000 Pa by controlling the airflow, the catalyst moving speed and the like.
In one embodiment of the present application, the sulfur-containing gas and the catalyst are cooled after separation, preferably by using water, heat transfer oil or steam. The industrial continuity is realized, and the running cost is reduced as much as possible.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The device shown in fig. 1 is adopted to perform catalytic reduction reaction of the sulfur dioxide-containing flue gas and the reducing gas in a mode of cross-flow contact with the catalyst, and sulfur-containing gas and the catalyst are continuously separated while the catalytic reduction reaction is performed to obtain sulfur.
The main composition of the sulphur dioxide containing flue gas is shown in table 1.
TABLE 1
| Components | Steam of water | Carbon dioxide | Sulfur dioxide |
| The weight percentage content | 22.5％ | 15％ | 5％ |
Wherein the catalyst is commercial shaped block activated carbon, the residence time of the flue gas containing sulfur dioxide in the reaction zone 16 is 4-6 s, and the continuous downward slow moving speed of the catalyst is 0.1-0.5 m/s; the catalyst inlet 03 and the catalyst outlet 05 are protected by nitrogen; the reaction temperature of the reaction zone 16 is 650-700 ℃; the thickness of the catalyst along the flowing direction of the flue gas containing sulfur dioxide is 1 m; the temperature of the introduced flue gas containing sulfur dioxide is between 650 and 700 ℃; the temperature of introduced reducing gas is between 650 and 700 ℃; the reducing gas is CO, the heat exchange medium in the two heat exchangers is water, and the flow resistance of the flue gas containing sulfur dioxide is between 800 and 1200 Pa.
And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 80 percent.
Example 2
The residence time of the flue gas containing sulfur dioxide in the reaction zone 16 is 7-10 s, the flow resistance of the flue gas containing sulfur dioxide is 100-600 Pa, and the rest is the same as that in the embodiment 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 84%.
Example 3
The retention time of the flue gas containing sulfur dioxide in the reaction zone 16 is 12-15 s, the flow resistance of the flue gas containing sulfur dioxide is 100-400 Pa, and the rest is the same as that of the embodiment 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 86%.
Example 4
The catalyst continuously moves downwards slowly at a speed of 0.05-1 m/h, otherwise the same as example 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 78%.
Example 5
The catalyst continuously moves downwards slowly at a speed of 0.5-1 m/s, otherwise the same as example 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 82%.
Example 6
The reaction temperature of the reaction zone 16 is 700-800 ℃, and the temperature of the introduced flue gas containing sulfur dioxide is 700-800 ℃; the temperature of introduced reducing gas is 700-800 ℃, and the rest is the same as that of the embodiment 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 88 percent.
Example 7
The reaction temperature of the reaction zone 16 is 200-400 ℃, and the temperature of the introduced flue gas containing sulfur dioxide is 200-400 ℃; the temperature of the introduced reducing gas is 200-400 ℃, and the method is the same as that of the embodiment 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 40%. Due to the lower reaction temperature, the conversion rate of sulfur dioxide is reduced, and the conversion rate of sulfur dioxide can be improved by prolonging the residence time of the reaction zone.
Example 8
The thickness of the catalyst is 3m along the flowing direction of the flue gas containing the sulfur dioxide, the flowing resistance of the flue gas containing the sulfur dioxide is 1400-1800 Pa, and the rest is the same as that of the catalyst in the embodiment 1. The concentration of outlet sulfur dioxide is detected by a gas chromatography-mass spectrometer analyzer, and the conversion rate of the sulfur dioxide is calculated to be 83 percent.
Example 9
The thickness of the catalyst is 0.5m along the flowing direction of the flue gas containing sulfur dioxide, the flowing resistance of the flue gas containing sulfur dioxide is between 200 and 600Pa, and the rest is the same as that of the catalyst in the embodiment 1. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 68 percent.
Example 10
Reducing gas to CH4Otherwise, the same procedure as in example 1 was repeated. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 65 percent.
Example 11
Reducing gas to H2Otherwise, the same procedure as in example 1 was repeated. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 60 percent.
Example 12
The catalyst is commercial shaped block activated carbon, the residence time of the flue gas containing sulfur dioxide in the reaction zone 16 is 2-3 s, and the continuous downward slow moving speed of the catalyst is 0.1-0.5 m/s; the reaction temperature of the reaction zone 16 is 650-700 ℃; the thickness of the catalyst along the flowing direction of the flue gas containing sulfur dioxide is 1 m; the temperature of the introduced flue gas containing sulfur dioxide is between 650 and 700 ℃; the temperature of introduced reducing gas is between 650 and 700 ℃; the reducing gas is CO, the heat exchange medium in the two heat exchangers is water, and the flow resistance of the flue gas containing sulfur dioxide is 2000-2500 Pa. And detecting the concentration of outlet sulfur dioxide by a gas chromatography-mass spectrometry analyzer, and calculating the conversion rate of the sulfur dioxide to be 56 percent. Because the catalyst after adsorption is not protected by nitrogen in the separation process, air is easy to leak into the device, reducing gas is easy to preferentially react with oxygen, and meanwhile, the active carbon also has a combustion reaction with the oxygen, so that the conversion efficiency of sulfur dioxide is low.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the catalyst inlet is arranged on the top wall of the reduction reaction chamber, so that the catalyst falls under the action of gravity; meanwhile, the sulfur dioxide-containing flue gas inlet and the reducing gas inlet are arranged on the side wall of the reduction reaction chamber, so that the airflow flows in the horizontal direction, the cross flow contact of the catalyst with the sulfur dioxide and the reducing gas is realized, the airflow resistance of the sulfur dioxide and the reducing gas is reduced, and the purposes of reaction and separation are realized on the basis of ensuring the contact time of the catalyst with the sulfur dioxide and the reducing gas. Therefore, the cross-flow moving device not only achieves the aim of reducing sulfur dioxide into sulfur with low energy consumption, but also achieves continuous reduction reaction and continuous separation of sulfur products, and is easy for industrial implementation.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A cross-flow moving device for continuously preparing sulfur from sulfur dioxide is characterized by comprising:
a reduction reaction chamber (10), wherein the reduction reaction chamber (10) is provided with a sulfur dioxide-containing flue gas inlet (01), a reduction gas inlet (02), a catalyst inlet (03), a sulfur-containing gas outlet (04) and a catalyst outlet (05), the sulfur dioxide-containing flue gas inlet (01), the reduction gas inlet (02) and the sulfur-containing gas outlet (04) are positioned on the side wall of the reduction reaction chamber (10), the catalyst inlet (03) is positioned on the top wall of the reduction reaction chamber (10), and the catalyst outlet (05) is positioned on the bottom wall of the reduction reaction chamber (10);
a catalyst supply unit (20) connected to the catalyst inlet (03) to supply a catalyst to the reduction reaction chamber (10);
a catalyst collection unit (30) connected to the catalyst outlet (05); and
and the sulfur collecting unit (40) is connected with the sulfur-containing gas outlet (04).
2. A cross-flow moving device according to claim 1, wherein the side walls of the reduction reaction chamber (10) comprise:
the gradually expanding wall (11), the sulfur dioxide-containing flue gas inlet (01) and the reducing gas inlet (02) are arranged at the beginning end of the gradually expanding wall (11);
a tapering wall (12) disposed opposite the tapering wall (11), the sulphur gas containing outlet (04) being disposed at an end of the tapering wall (12); and
a main side wall (13) connected between the diverging wall (11) and the converging wall (12).
3. Cross-flow moving device according to claim 2, wherein inside the reduction reaction chamber (10) is arranged:
the first gas distributor (14) is fixedly arranged at the joint of the gradually expanding wall (11) and the main side wall (13);
a second gas distributor (15) fixedly arranged at the connection of the tapered wall (12) and the main side wall (13); and
a reaction zone (16) disposed between the first gas distributor (14) and the second gas distributor (15).
4. The cross-flow moving device according to claim 1, wherein the catalyst collection unit (30) comprises:
the catalyst collecting tank (31) is arranged below the reduction reaction chamber (10), and the wall of the catalyst collecting tank (31) is connected with the side wall of the reduction reaction chamber (10);
the first heat exchanger (32) is connected and arranged below the catalyst collecting tank (31);
and a catalyst on-off valve (33) disposed on a pipeline between the catalyst collection tank (31) and the heat exchanger.
5. The cross-flow movement apparatus according to claim 1, wherein the sulphur collection unit (40) comprises:
the second heat exchanger (41) is connected with the sulfur-containing gas outlet (04);
a sulfur collector (42) which is arranged at the downstream of the second heat exchanger (41) and is connected with the sulfur-containing gas outlet (04) through the second heat exchanger (41).
6. The cross-flow moving device according to claim 1, wherein the catalyst supply unit (20) comprises:
and the catalyst storage bin (21) is arranged above the reduction reaction chamber (10), and a catalyst blanking valve (22) is arranged on a connecting pipeline between the catalyst storage bin and the catalyst inlet (03).
7. A method for continuously preparing sulfur from sulfur dioxide, which is implemented by using the cross-flow moving device for continuously preparing sulfur from sulfur dioxide according to claim 1, and comprises the following steps:
carrying out catalytic reduction reaction on the flue gas containing sulfur dioxide and reducing gas in a mode of cross-flow contact with a catalyst to obtain sulfur-containing gas, and continuously separating the sulfur-containing gas from the catalyst while the catalytic reduction reaction is carried out to obtain the sulfur.
8. The method according to claim 7, characterized in that the catalytic reduction reaction is carried out inside a reduction reaction chamber (10), the side walls of the reduction reaction chamber (10) comprising:
the initial end of the gradually expanding wall (11) is provided with a sulfur dioxide-containing flue gas inlet (01) and a reducing gas inlet (02);
the reducing wall (12) is arranged opposite to the expanding wall (11), and the tail end of the reducing wall (12) is provided with a sulfur-containing gas outlet (04); and
a main side wall (13) connected between the diverging wall (11) and the converging wall (12).
9. The method according to claim 8, characterized in that inside the reduction reaction chamber (10) there are provided:
a first gas distributor (14) arranged at the junction of the diverging wall (11) and the main side wall (13);
a second gas distributor (15) arranged at the junction of the tapered wall (12) and the main side wall (13); and
a reaction zone (16) disposed between the first gas distributor (14) and the second gas distributor (15), the catalytic reduction reaction occurring within the reaction zone (16).
10. The method according to claim 9, wherein the catalyst is selected from any one of activated carbon and activated coke.
11. The method of claim 10, wherein the reducing gas is H2、CH4And CO.
12. The process according to claim 9, wherein the catalyst is moved at a speed of between 0.05m/h and 1 m/s.
13. A method according to claim 12, characterized in that the residence time of the sulphur dioxide containing flue gas in the reaction zone (16) is between 4 and 15 s.
14. The method according to claim 12, wherein the thickness of the catalyst in the flow direction of the sulphur dioxide comprising flue gas is between 0.5 and 3 m.
15. The method according to claim 12, characterized in that the catalyst enters and/or exits the reduction reaction chamber (10) under nitrogen or inert gas protection.
16. The method according to claim 9, wherein the reaction temperature of the catalytic reduction reaction is between 200 and 800 ℃, and the flow resistance of the flue gas containing sulfur dioxide in the reaction zone (16) is controlled to be between 200 and 2000 Pa.
17. The method of claim 7, wherein the sulfur-containing gas and the catalyst are separately cooled after separation.
18. The method of claim 17, wherein the temperature reduction is performed using water, thermal oil, or steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810168167.7A CN108516524B (en) | 2018-02-28 | 2018-02-28 | Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810168167.7A CN108516524B (en) | 2018-02-28 | 2018-02-28 | Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108516524A CN108516524A (en) | 2018-09-11 |
| CN108516524B true CN108516524B (en) | 2020-06-02 |
Family
ID=63433312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810168167.7A Active CN108516524B (en) | 2018-02-28 | 2018-02-28 | Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108516524B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435272A (en) * | 2002-01-29 | 2003-08-13 | 国家电站燃烧工程技术研究中心 | Moving-bed active coke desulfurating and sulfur reutilization method |
| CN201692766U (en) * | 2010-03-19 | 2011-01-05 | 东南大学 | Device for removing hazardous constituents from cement kiln flue gas by utilizing cross-flow moving bed |
| CN102631905A (en) * | 2012-03-23 | 2012-08-15 | 太原钢铁(集团)有限公司 | Desulfurized activated carbon regenerating column and method |
| CN204778829U (en) * | 2015-06-03 | 2015-11-18 | 中国海洋石油总公司 | Sulphur recovery unit |
| CN106753494A (en) * | 2016-12-07 | 2017-05-31 | 神华集团有限责任公司 | Activated coke preparation facilities and method |
-
2018
- 2018-02-28 CN CN201810168167.7A patent/CN108516524B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435272A (en) * | 2002-01-29 | 2003-08-13 | 国家电站燃烧工程技术研究中心 | Moving-bed active coke desulfurating and sulfur reutilization method |
| CN201692766U (en) * | 2010-03-19 | 2011-01-05 | 东南大学 | Device for removing hazardous constituents from cement kiln flue gas by utilizing cross-flow moving bed |
| CN102631905A (en) * | 2012-03-23 | 2012-08-15 | 太原钢铁(集团)有限公司 | Desulfurized activated carbon regenerating column and method |
| CN204778829U (en) * | 2015-06-03 | 2015-11-18 | 中国海洋石油总公司 | Sulphur recovery unit |
| CN106753494A (en) * | 2016-12-07 | 2017-05-31 | 神华集团有限责任公司 | Activated coke preparation facilities and method |
Non-Patent Citations (2)
| Title |
|---|
| "Reduction of SO2 to elemental sulfur with H2 and mixed H2/CO gas in an activated carbon bed";Tai Feng etal;《chemicalEngineeringResearchAndDesign》;20170321;第121卷;第192页第2部分反应系统 * |
| "气固错流移动床高温煤气脱硫过程模拟";赵建涛等;《煤炭转化》;20030825;第26卷(第3期);第40-44页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108516524A (en) | 2018-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102000486B (en) | Method for catching carbon dioxide in flue gas by active sodium carbonate and apparatus thereof | |
| CN102631905B (en) | Desulfurized activated carbon regenerating column and method | |
| CN101519193B (en) | Acid preparing method by coal gas wet oxidation and desulfurization | |
| CN111495111A (en) | Low temperature fixed bed integration adsorbs SOx/NOx control system | |
| CN101224387B (en) | Circulating fluid bed flue gas desulfurization process and device thereof | |
| CN105233673A (en) | Carbon-based catalyst desulfurization and denitrification system and method | |
| CN103980953A (en) | Coke oven gas desulfurization process and device | |
| CN103980955B (en) | Coal gas desulfurization and sulfur regeneration technique and device | |
| CN211988670U (en) | Pollutant comprehensive treatment system suitable for large coal-fired power plant | |
| CN101810981B (en) | Efficient low-resistance cross-flow type moving bed desulfurizing tower | |
| CN103172087A (en) | Method for preparing sulfuric acid or ammonium sulfate from coal gas wet oxidative desulfurization sulfur pulp | |
| CN108704464B (en) | Comprehensive treatment system and process for desulfurization and denitrification of sintering flue gas and whitening of flue gas | |
| CN108786441B (en) | Sulfur preparation process by electromigration desulfurization of coke oven flue gas | |
| CN101920166B (en) | Denitration method for desulfurization postposition | |
| CN108516524B (en) | Cross flow moving device and method for continuously preparing sulfur by sulfur dioxide | |
| CN204522707U (en) | Electron beam flue gas processing device | |
| CN110038646B (en) | Carbon-based catalyst regeneration device and process | |
| CN207667663U (en) | Two-part carbon base catalyst regenerates Tower System | |
| CN110694470A (en) | System and method for flue gas desulfurization and denitration by using methane | |
| CN207371539U (en) | Three-stage carbon base catalyst regenerates Tower System | |
| CN216614549U (en) | Blast furnace gas desulfurization and dechlorination purification device | |
| CN210934478U (en) | System for flue gas desulfurization and denitration are carried out with methane | |
| CN210357199U (en) | Carbon-based catalyst regenerating unit | |
| CN112852504A (en) | System and process for prolonging service life of blast furnace gas fine desulfurization reactant | |
| CN208742253U (en) | A kind of double adjusting duct type desulfurizers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |