CN218901381U - Treatment system for gas containing hydrogen sulfide - Google Patents
Treatment system for gas containing hydrogen sulfide Download PDFInfo
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- CN218901381U CN218901381U CN202222886291.1U CN202222886291U CN218901381U CN 218901381 U CN218901381 U CN 218901381U CN 202222886291 U CN202222886291 U CN 202222886291U CN 218901381 U CN218901381 U CN 218901381U
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- 239000007789 gas Substances 0.000 title claims abstract description 180
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 103
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 90
- 239000011593 sulfur Substances 0.000 claims abstract description 89
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 31
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
- 238000000746 purification Methods 0.000 claims abstract description 15
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 72
- 238000001816 cooling Methods 0.000 claims description 53
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003546 flue gas Substances 0.000 abstract description 15
- 150000002431 hydrogen Chemical class 0.000 abstract description 8
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The utility model relates to the technical field of sulfur-containing flue gas treatment, and discloses a treatment system for hydrogen sulfide-containing gas. The system comprises a thermal reaction unit (1), a catalytic reaction unit (2), a tail gas purification unit (3) and an adsorption unit (4) which are connected in sequence; the adsorption unit (4) comprises a connected moving adsorbent bed (41) loaded with adsorbent, a regenerator (42) and a lifting device (43). The system adopts the movable adsorption bed to carry out SO on the incineration tail gas 2 Adsorption, namely, SO is carried out on flue gas of a sulfur device 2 The discharge concentration is reduced to less than or equal to 10mg/m 3 Near zero emission is realized, and the hydrogen sulfide-removed tail gas containing hydrogen from the absorption tower is used as a regeneration gas source of the adsorbent, so that the use loss of the adsorbent can be effectively reduced. The system realizes the closed cycle of sulfur resources in the treatment process, and the total sulfur recovery rate is obviously improved.
Description
Technical Field
The utility model relates to the technical field of sulfur-containing flue gas treatment, in particular to a treatment system for hydrogen sulfide-containing gas.
Background
In the prior sulfur device, the sulfur recovery device is not only a production device used as an end process, but also a ring protection device. The emission standard of petroleum refining industrial pollutants (GB 31570-2015) puts more strict requirements on the emission of sulfur plant flue gas: the emission concentration limit value of the sulfur dioxide in the flue gas of the sulfur device generally meets the regional requirement of 400mg/Nm 3 In the following, the requirement of the important area reaches 100mg/Nm 3 The following is given.
In the prior main process of domestic sulfur recovery, the technology is LS-DeGAS complete set technology for reducing sulfur dioxide emission of sulfur recovery device of China petrochemical Qilu division company, and can reduce the concentration of sulfur dioxide emission of flue gas of the sulfur device to 100mg/Nm 3 The technology has the following problems that the sulfur recovery device is difficult to stably discharge after reaching standards for a long time; the other type of process is an alkali liquor absorption method, and the high-concentration salt-containing wastewater produced by the process has stronger corrosiveness, so that the device cannot stably operate for a long time, and the salt-containing wastewater needs to be treated, so that the process is complicated, the treatment difficulty is high, and the cost is increased.
Therefore, the problems that the emission concentration of the flue gas sulfur dioxide is high and the long-term operation stability of the device is difficult in the existing sulfur recovery process are needed to be solved.
Disclosure of Invention
Aiming at the problems that the emission concentration of the flue gas sulfur dioxide is still higher and the device is difficult to stably operate for a long time in the existing sulfur recovery process, the utility model provides a treatment system for the gas containing hydrogen sulfide.
In order to achieve the above object, the present utility model provides a treatment system for a hydrogen sulfide-containing gas, characterized in that the system comprises a thermal reaction unit, a catalytic reaction unit, an exhaust gas purification unit and an adsorption unit, which are sequentially connected;
the thermal reaction unit is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
the catalytic reaction unit is used for carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
the tail gas purification unit is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the Claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two streams of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
the adsorption unit comprises a movable adsorption bed, a regenerator and a lifting device which are connected and loaded with an adsorbent, and is used for carrying out adsorption sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
the movable adsorption bed comprises a storage material layer, an adsorption layer and a unloading layer which are sequentially arranged from top to bottom;
the regenerated adsorbent is circulated back to the moving adsorbent bed, and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit, the catalytic reaction unit and the tail gas purification unit.
Preferably, the thermal reaction unit comprises a sulfur producing furnace and a first cooling device which are connected in sequence.
Preferably, the catalytic reaction unit comprises a primary converter and a secondary converter which are connected in sequence; wherein the primary converter is connected to the first cooling device.
Preferably, the catalytic reaction unit further comprises a second cooling device and a third cooling device; wherein the second cooling device is respectively connected with the primary converter and the secondary converter; the third cooling device is connected with the secondary converter.
Preferably, the tail gas purifying unit comprises a hydrogenation device, an absorption tower and an incinerator which are connected in sequence; wherein the hydrogenation device is connected with the third cooling device.
Preferably, the tail gas purification unit further comprises a quenching tower, and the quenching tower is respectively connected with the hydrogenation device and the absorption tower.
Preferably, the adsorption unit further comprises a waste heat boiler, a first heat exchanger and a second heat exchanger which are sequentially connected; wherein,,
the waste heat boiler is connected with the incinerator;
the first heat exchanger is respectively connected with the absorption tower and the regenerator;
the second heat exchanger is connected with the movable adsorption bed.
Preferably, in the moving adsorbent bed, the material layer is connected to the regenerator by a lifting device;
the adsorption layer is connected with the second heat exchanger;
the discharging layer is connected with the regenerator.
Preferably, the adsorption unit further comprises an auxiliary heater connected to the regenerator and the first heat exchanger, respectively.
Preferably, the regenerator is connected to at least one of the sulfur producing furnace, primary converter, secondary converter and hydrogenation unit.
Through the technical scheme, the treatment system for the hydrogen sulfide-containing gas has the following beneficial effects:
(1) The system provided by the utility model adopts the movable adsorption bed to carry out SO on the incineration tail gas 2 Adsorption, namely, SO is carried out on flue gas of a sulfur device 2 The discharge concentration is reduced to less than 10mg/m 3 Realizing near zero emission, preferably reaching SO 2 The discharge concentration is less than or equal to 5mg/m 3 ；
(2) The system provided by the utility model adopts the hydrogen-containing hydrogen sulfide removal tail gas from the absorption tower as a regeneration gas source of the adsorbent, so that the use loss of the adsorbent can be effectively reduced, and the loss of the adsorbent is less than or equal to 1wt%/1000h;
(3) The system provided by the utility model realizes the closed cycle of sulfur in the operation process, and the regenerated gas containing sulfur dioxide generated after the adsorbent regeneration can return to the sulfur recovery device of the system to continuously recover sulfur resources, so that the total sulfur recovery rate of the system is close to 100%; in addition, the system can fully utilize the waste heat generated by devices in the system, and effectively reduce the overall operation energy consumption of the system;
(4) The adsorption unit has less equipment, easy operation and control, low investment and no secondary pollution.
Drawings
The accompanying drawings are included to provide a further understanding of the utility model, and are incorporated in and constitute a part of this specification, illustrate the utility model and together with the description serve to explain, without limitation, the utility model. In the drawings:
FIG. 1 is a schematic view of a treatment system for a hydrogen sulfide containing gas according to one embodiment of the present utility model.
Description of the reference numerals
1-thermal reaction unit 2-catalytic reaction unit 3-tail gas purifying unit
4-adsorption unit 11-sulfur-producing furnace 12-first cooling device
21-primary converter 22-secondary converter 23-second cooling device
24-third cooling device 31-hydrogenation device 32-fourth cooling device
33-quench tower 34-absorber tower 35-incinerator
36-Claus tail gas heater 41-moving adsorbent bed 411-reservoir
412-adsorption layer 413-discharge layer 42-regenerator
43 lifting device 44 waste heat boiler 45 first heat exchanger
46-second heat exchanger 47-auxiliary heater 48-chimney
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The utility model provides a treatment system for hydrogen sulfide-containing gas, which is shown in figure 1, and comprises a thermal reaction unit 1, a catalytic reaction unit 2, a tail gas purification unit 3 and an adsorption unit 4 which are connected in sequence;
the thermal reaction unit 1 is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
the catalytic reaction unit 2 is used for carrying out a claus conversion reaction on the process gas to obtain sulfur and claus tail gas;
the tail gas purifying unit 3 is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two streams of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
the adsorption unit 4 comprises a movable adsorption bed 41, a regenerator 42 and a lifting device 43 which are connected and used for carrying out adsorption sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
wherein, the movable adsorption bed 41 comprises a storage layer 411, an adsorption layer 412 and a discharge layer 413 which are sequentially arranged from top to bottom;
the regenerated adsorbent is circulated back to the moving adsorbent bed 41, and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit 1, the catalytic reaction unit 2, and the exhaust gas purification unit 3.
In the present utility model, the hydrogen sulfide-containing gas refers to H-containing gas generated in the fields of natural gas purification, refining and coal chemical industry 2 S gas, its composition includes H 2 S、CO 2 、H 2 O、NH 3 And hydrocarbons, etc. Preferably, in the hydrogen sulfide-containing gas, H 2 The S content is 30-90% by volume, preferably 50-85% by volume.
According to the utility model, the thermal reaction unit 1 comprises a sulfur producer 11 and a first cooling device 12 connected in sequence. In the present utility model, in the thermal reaction unit 1, the hydrogen sulfide-containing gas is first introduced into the sulfur producing furnace 11 and mixed with air for combustion to obtainContaining S, H 2 S、SO 2 COS and CS 2 Is a hot reaction product gas of (a); the hot reaction product gas is then introduced into the first cooling means 12 for condensation, wherein S is condensed and separated as elemental sulfur, preferably into a liquid sulfur pool outside the boundary zone. The hot reaction product gas after separation of elemental sulphur, i.e. the process gas, leaves the first cooling means 12 and enters the catalytic reaction unit 2.
In the process gas, preferably H 2 The content of S is 3-10v%; SO (SO) 2 The content of (2) is 1.5-5v%; the COS content is 0.2-1v%.
In the present utility model, the sulfur producing furnace 11 is not particularly limited, and a sulfur producing combustion furnace which is conventional in the art may be used.
According to the present utility model, the catalytic reaction unit 2 includes a primary converter 21 and a secondary converter 22 connected in sequence; wherein the primary converter 21 is connected to the first cooling device 12.
In the present utility model, in the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 sequentially enters a multistage converter to perform a claus conversion reaction, preferably using two stages of conversion. Specifically, the process gas enters a primary converter 21, the primary converter 21 carries a first sulfur recovery catalyst, and in the presence of the first sulfur recovery catalyst, H in the process gas 2 S and SO 2 Generating elemental sulfur, COS and CS by the Claus reaction 2 Hydrolysis reaction takes place to generate H 2 S, obtaining a first-stage conversion reaction product containing sulfur; the primary conversion reaction product is subjected to sulfur separation and then enters the secondary converter 22, the secondary converter 22 is loaded with a second sulfur recovery catalyst, and H in the primary conversion reaction product exists in the presence of the second sulfur recovery catalyst 2 S and SO 2 And (3) continuously carrying out a Claus reaction to generate elemental sulfur, obtaining a sulfur-containing secondary conversion reaction product, separating sulfur to obtain Claus tail gas, and entering the tail gas purifying unit 3. The Claus tail gas contains H 2 S、SO 2 、COS、CS 2 And a trace amount of S.
In the claus tail gas, preferably H, according to the utility model 2 The content of S is 0.5-2v%; SO (SO) 2 The content of (2) is 0.3-1v%; the COS content is 0.01-0.05v%.
According to the present utility model, the first sulfur recovery catalyst and the second sulfur recovery catalyst may be claus conversion reaction catalysts conventional in the art, and may each be independently selected from at least one of a oxygen-leaking type sulfur recovery catalyst, a titanium oxide-based sulfur recovery catalyst, and an alumina-based sulfur recovery catalyst. In the utility model, the first sulfur recovery catalyst and the second sulfur recovery catalyst can be obtained by adopting conventional commercial brand products or by adopting a conventional method.
According to the utility model, the catalytic reaction unit 2 further comprises second cooling means 23 and third cooling means 24; wherein the second cooling device 23 is connected to the primary converter 21 and the secondary converter 22, respectively; the third cooling device 24 is connected to the secondary converter 22.
In the present utility model, the second cooling device 23 is configured to condense the primary conversion reaction product, and separate S from the primary conversion reaction product; the third cooling device 24 is used for condensing the secondary conversion reaction product and separating S in the secondary conversion reaction product. S separated from the primary conversion reaction product and the secondary conversion reaction product is preferably discharged into a liquid sulfur pool outside the boundary region.
In the present utility model, the first cooling device 12, the second cooling device 23, and the third cooling device 24 are not particularly limited, and cooling separation devices conventional in the art may be employed.
According to the present utility model, the exhaust gas purifying unit 3 includes a hydrogenation apparatus 31, an absorption tower 34, and an incinerator 35, which are sequentially connected; wherein the hydrogenation unit 31 is connected to the third cooling unit 24.
In the present utility model, in the exhaust gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is first introduced into the hydrogenation apparatus 31, whereHydrogenation reaction occurs under the action of hydrogenation catalyst, and SO in the Claus tail gas 2 、COS、CS 2 And S and the like to H 2 S, obtain H-containing 2 S, hydrogenation tail gas; thereafter said H-containing 2 S hydrogenation tail gas is introduced from the lower part of the absorption tower 34, gas is in countercurrent contact with the desulfurizing absorbent in the absorption tower 34 in the rising process, and H in the gas 2 S is absorbed by a desulfurization absorbent, and hydrogen sulfide-removed tail gas containing hydrogen is obtained at the top of the absorption tower 34; the hydrogen-containing hydrogen sulfide removal tail gas is divided into two parts, namely hydrogen-containing hydrogen sulfide removal tail gas-I and hydrogen-containing hydrogen sulfide removal tail gas-II, and the hydrogen-containing hydrogen sulfide removal tail gas-I enters the incinerator 35 for incineration treatment to obtain the incineration tail gas containing sulfur dioxide. The hydrogen sulfide-removed tail gas-II and the incineration tail gas containing hydrogen respectively enter the adsorption unit 4 from different lines.
In the utility model, the hydrogen-containing hydrogen sulfide removal tail gas contains H 2 Small amount of residual H 2 S and COS. Preferably, in the hydrogen-containing hydrogen sulfide removal tail gas, H 2 The content of (2-8 v%, preferably 3-5v%; h 2 S content is 5-200ppm; the COS content is 2-100ppm.
In the utility model, the incineration tail gas contains water vapor and O 2 、SO 2 、N 2 、CO 2 And CO, etc. Preferably, in the incineration tail gas, SO 2 The content of (C) is 50-1000mg/m 3 Preferably 50-500mg/m 3 。
According to the present utility model, the exhaust gas purifying unit 3 further includes a quenching tower 33, and the quenching tower 33 is connected to the hydrogenation apparatus 31 and the absorption tower 34, respectively.
In the present utility model, the quenching tower 33 is used for quenching the H-containing stream from the hydrogenation unit 31 2 And (3) cooling the hydrogenated tail gas of the S. Preferably, a fourth cooling device 32, i.e. the H-containing device, is arranged before the quenching tower 33 2 The hydrogenated tail gas of S passes through the fourth cooling device 32 and the quenching tower 33 in sequence, and enters the absorption tower 34 after being cooled down.
According to the utility model, a claus tail gas heater 36 is preferably provided in the connection between the third cooling unit 24 and the hydrotreater 31 for preheating the claus tail gas prior to the hydrotreatment.
In the present utility model, the hydrogenation apparatus 31, the fourth cooling apparatus 32, the quenching tower 33, the absorption tower 34, the incinerator 35, and the claus tail gas heater 36 are not particularly limited, and may be selected by any apparatuses commonly used in the art.
According to the utility model, the adsorption unit 4 further comprises a waste heat boiler 44, a first heat exchanger 45 and a second heat exchanger 46, which are connected in sequence. Wherein the waste heat boiler 44 is connected to the incinerator 35; the first heat exchanger 45 is connected to the absorber 34 and the regenerator 42, respectively; the second heat exchanger 46 is connected to the moving adsorbent bed 41.
According to the present utility model, for the connection mode of the first heat exchanger 45 and the absorption tower 34, specifically, the first heat exchanger 45 is connected to the product gas outlet at the top of the absorption tower 34.
According to the present utility model, in the moving adsorbent bed 41, the storage layer 411, the adsorption layer 412 and the discharge layer 413 are separated by using openable and closable separation baffles, so as to form a storage functional area, an adsorption functional area and a discharge functional area, respectively. Specifically, the storage layer 411 is configured to store fresh adsorbent or regenerated adsorbent after regeneration, an adsorbent inlet is provided at the upper portion of the storage layer 411, and a separation baffle between the bottom and the adsorption layer 412 can be opened and closed to realize unloading of the adsorbent stored in the storage layer 411 to the adsorption layer 412; the adsorption layer 412 is used for performing adsorption sulfur dioxide removal treatment by contacting incineration tail gas with an adsorbent, the adsorption layer 412 is provided with an air inlet and an air outlet, the air inlet is positioned at the lower part of the adsorption layer 412, the air outlet is positioned at the upper part of the adsorption layer 412, and an isolation baffle between the bottom of the adsorption layer 412 and the discharge layer 413 can be opened and closed to realize discharge of the adsorbent to be regenerated generated by the adsorption layer 412 to the discharge layer 413; the discharging layer 413 is used for storing the adsorbent to be regenerated, which is saturated by adsorption of sulfur dioxide from the adsorption layer 412.
In the present utility model, the regenerator 42 is provided with an adsorbent regeneration chamber, an adsorbent inlet to be regenerated, and a regenerated adsorbent outlet; the regenerator 42 is provided with a heating coil, and the adsorbent can be regenerated by supplying heat to the adsorbent to be regenerated and raising the temperature through introducing a heat medium into the heating coil.
According to the utility model, the storage layer 411 is connected to the regenerator 42 by means of a lifting device 43. As for the connection manner of the storage material layer 411 and the regenerator 42, specifically, the storage material layer 411 is connected to a regenerated adsorbent outlet of the regenerator 42 through a lifting device 43.
According to the present utility model, the adsorption layer 412 is coupled to the second heat exchanger 46. For the connection mode between the adsorption layer 412 and the second heat exchanger 46, specifically, the air inlet and the air outlet of the adsorption layer 412 are respectively connected to the second heat exchanger 46.
According to the utility model, the discharge layer 413 is connected to the regenerator 42. As regards the connection of the discharge layer 413 to the regenerator 42, in particular, the discharge layer 413 is connected to the adsorbent inlet of the regenerator 42 to be regenerated.
In the present utility model, the adsorbent is at least one selected from the group consisting of activated carbon, activated coke, metal oxide and molecular sieve, preferably activated carbon.
In the present utility model, the metal oxide includes, but is not limited to, copper oxide, iron oxide, zinc oxide, or the like, preferably copper oxide.
In the present utility model, the molecular sieve includes, but is not limited to, an X-type molecular sieve, a Y-type molecular sieve, a NaY molecular sieve, or the like, preferably a NaY molecular sieve.
In the present utility model, preferably, the initial sulfur capacity of the adsorbent is 100 to 250g sulfur per 1000g adsorbent.
According to the utility model, SO in the purified gas obtained by adsorption sulfur dioxide removal treatment by the movable adsorption bed 41 2 The content of (2) is less than or equal to 10mg/m 3 Preferably 5mg/m or less 3 。
According to the present utility model, the adsorption unit 4 may further include an auxiliary heater 47, and the auxiliary heater 47 is connected to the regenerator 42 and the first heat exchanger 45, respectively. Wherein, for the connection mode of the auxiliary heater 47 and the regenerator 42, specifically, the auxiliary heater 47 is connected with at least a heating coil of the regenerator 42.
According to a preferred embodiment of the present utility model, for the connection of the auxiliary heater 47 and the regenerator 42, it is preferable that the auxiliary heater 47 is connected to the heating coil of the regenerator 42 and the adsorbent regeneration chamber, respectively.
According to the utility model, the regenerator 42 may also be connected to the first heat exchanger 45 by means of a circulating heating line. Wherein, for the connection mode of the cyclic heating line and the regenerator 42, specifically, the cyclic heating line is connected with a heating coil of the regenerator 42.
According to the present utility model, the regenerator 42 is connected to at least one of the sulfur producing furnace 11, the primary converter 21, the secondary converter 22, and the hydrogenation apparatus 31.
In the present utility model, the working process of the adsorption unit 4 may be divided into two stages of desulfurization adsorption of incineration tail gas and cyclic regeneration of adsorbent, which are specifically described as follows:
1. desulfurization adsorption of incineration tail gas
The incineration tail gas from the incinerator 35 and the hydrogen-containing hydrogen sulfide removal tail gas-II from the top of the absorption tower 34 enter an adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling, then exchanges heat and cools with the hydrogen-containing hydrogen sulfide removal tail gas-II in the first heat exchanger 45, continuously exchanges heat and cools with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, and finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41; the cooled incineration tail gas moves from bottom to top in the adsorption layer 412, contacts with the adsorbent to perform multistage adsorption, and the SO contained in the incineration tail gas 2 Is removed to obtain purified gas and is led out from the gas outlet of the adsorption layer 412, and then is connected with the incineration tail in the second heat exchanger 46The gas exchanges heat and heats up, and finally reaches the standard to be discharged through a chimney 48;
in the process of absorbing and removing sulfur dioxide from the incineration tail gas, preferably, the purification effect is monitored through an online analysis instrument of purified flue gas, and when SO in the purified gas 2 When the content is stable and no obvious rising trend exists, the content indicates that the sulfur capacity allowance of the adsorbent in the adsorption layer 412 is larger, and the adsorption can be continued; when purifying SO in gas 2 When the content is gradually increased and the rising trend is obvious, the residual sulfur capacity of the adsorbent is smaller, and the adsorbent needs to be regenerated and the fresh adsorbent needs to be replenished. At this time, the isolation barrier between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent is discharged to the discharge layer 413, and the isolation barrier between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is replenished to the adsorption layer 412 to continue adsorbing SO 2 。
2. Recycling regeneration of adsorbents
The adsorbent to be regenerated enters the regenerator 42 from the discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 exchanges heat with the incineration flue gas in the first heat exchanger 45 to raise the temperature, and preferably is heated and raised by the auxiliary heater 47, and enters the regenerator 42 to serve as a regeneration heat source of the adsorbent to be regenerated, the regenerated adsorbent is subjected to heat regeneration treatment, the obtained regenerated adsorbent is sent to the storage layer 411 through the lifting device 43 to be recycled, and the obtained regenerated gas containing high-concentration sulfur dioxide is introduced into at least one of the sulfur making furnace 11, the primary converter 21, the secondary converter 22 and the hydrogenation device 31 to repeatedly recycle sulfur.
Preferably, the hydrogen-containing hydrogen sulfide removal tail gas-II is divided into two lines and enters the regenerator 42, one line enters a heating coil of the regenerator 42 to heat the regenerator 42 for heating and thermally regenerating the adsorbent, and then is led out from the heating coil, enters a circulating heating line, and enters the heating coil for recycling after being heated in sequence by the first heat exchanger 45 and the auxiliary heater 47; the other path of the solution enters an adsorbent regeneration chamber for carrying SO which is thermally regenerated and desorbed 2 The gas enters the sulfur making furnace 11 and the primary converter21. At least one of the secondary converter 22 and the hydrogenation unit 31.
According to the utility model, the regeneration gas containing sulphur dioxide is preferably returned to the primary converter 21.
In accordance with the present utility model, the regenerated sorbent is preferably cooled down using a portion of the hydrogen-containing hydrogen sulfide depleted gas-II from the top of absorber column 34 before the cooled regenerated sorbent is sent to storage layer 411.
The following describes the processing procedure and effects of the system for processing the hydrogen sulfide-containing gas in conjunction with the system for processing the hydrogen sulfide-containing gas shown in fig. 1 provided by the present utility model.
1. Raw material acquisition:
hydrogen sulfide-containing gas H 2 S 80v％、CO 2 10v％、H 2 O 5v％、NH 3 4v% and 1v% hydrocarbons, produced by a natural gas purification process;
first sulfur recovery catalyst: the oxygen leakage-free sulfur recovery catalyst (with the brand of LS-971 and purchased from Shandong Ji Luke chemical industry institute Co., ltd.) and the titanium oxide-based sulfur recovery catalyst (with the brand of LS-981G and purchased from Shandong Ji Luke chemical industry Co., ltd.) are mixed according to the volume ratio of 1:2, compounding to obtain the compound;
first sulfur recovery catalyst: alumina-based sulfur recovery catalyst, brand LS-02, available from Shandong Qilu chemical industry institute of GmbH;
hydrogenation catalyst: the brand LSH-03A was purchased from Shandong Ji Luke force chemical industry institute Co., ltd.
Desulfurization adsorbent (exhaust gas purifying unit): MDEA solution with a concentration of 45 wt%.
Adsorbent (adsorption unit): activated carbon with an initial sulfur capacity of 160g sulfur per 1000g adsorbent.
2. The working process of the treatment system containing hydrogen sulfide gas comprises the following steps:
(1) In the thermal reaction unit 1, the hydrogen sulfide-containing gas was mixed with air in the sulfur producing furnace 11 and burned (temperature 1300 ℃ C.; space velocity 1000 h) -1 ) The obtained hot reaction product gas enters into the firstCondensing by a cooling device 12, and discharging the cooled elemental sulfur into a liquid sulfur pool outside the boundary region to obtain liquid sulfur; at the outlet of the first cooling device 12 a process gas (H is obtained 2 The S content was 6.39v%; SO (SO) 2 Is 3.26v%; the content of COS is 0.39 v%;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, and a primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 315 ℃ C.; the space velocity is 1000 h) -1 ) The obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside the boundary region to obtain liquid sulfur; the product of the primary conversion reaction from which sulfur was separated was fed to a secondary converter 22, and subjected to a secondary conversion reaction in the presence of a second sulfur recovery catalyst (reaction temperature: 250 ℃ C.; space velocity: 1000 h) -1 ) The obtained sulfur-containing secondary conversion reaction product enters a third cooling device 24 for condensation, elemental sulfur is discharged into a liquid sulfur pool outside the boundary region after cooling to obtain liquid sulfur, and claus tail gas (H) is obtained at the outlet of the third cooling device 24 2 The content of S is 1.12v%; SO (SO) 2 The content of (2) is 0.58v%; the content of COS is 0.04 v%;
(3) In the exhaust gas purifying unit 3, the claus exhaust gas from the catalytic reaction unit 2 was preheated to 250 ℃ by a claus exhaust gas heater 36, and then fed to the hydrogenation apparatus 31, and hydrogenation reaction was carried out in the presence of a hydrogenation catalyst (the reaction temperature was 280 ℃; space velocity was 1000 h) -1 ) Obtaining H-containing 2 S, hydrogenation tail gas; containing H 2 The hydrogenated tail gas of S is cooled to 38 ℃ by a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent, and hydrogen-containing hydrogen sulfide-removed tail gas (H) is obtained at the top of the absorption tower 34 2 Is 4.5v%; h 2 The S content is 68ppm; the COS content was 16 ppm); dividing the hydrogen-containing hydrogen sulfide removal tail gas into two parts, namely hydrogen-containing hydrogen sulfide removal tail gas-I and hydrogen-containing hydrogen sulfide removal tail gas-II (the volume ratio of the hydrogen-containing hydrogen sulfide removal tail gas-I to the hydrogen-containing hydrogen sulfide removal tail gas-II is 35:1), wherein the hydrogen-containing hydrogen sulfide removal tail gas-I enters an incinerator 35 for incinerationTreating (temperature 680 ℃ C.; airspeed 1000 h) -1 ) To produce incineration tail gas (SO) containing sulfur dioxide 2 Is 238mg/m 3 )；
The hydrogen sulfide-removed tail gas-II and the incineration tail gas containing hydrogen enter an adsorption unit 4 respectively from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling (cooling to 250 ℃), then passes through the first heat exchanger 45 for heat exchange and cooling (cooling to 200 ℃) with the hydrogen-containing dehydrosulfuration tail gas-II, further passes through the second heat exchanger 46 for heat exchange and cooling (cooling to 100 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, and the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with the activated carbon adsorbent (the initial sulfur capacity is 160g sulfur/1000 g adsorbent) for adsorption and sulfur dioxide removal treatment (the adsorption temperature is 100 ℃, and the space velocity of the incineration tail gas is 1000 h) -1 ) Burning SO contained in tail gas 2 Is removed, and purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored through an online analysis instrument for purifying the flue gas, and when SO (sulfur dioxide) in the purified gas 2 When the content is stable and has no obvious rising trend, the adsorption can be continued; when purifying SO in gas 2 When the content is gradually increased and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to the regenerator 42 by a discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 exchanges heat with the incineration flue gas in a first heat exchanger 45 to raise the temperature,then the adsorbent is heated to 380 ℃ by an auxiliary heater 47 and then is divided into two lines to enter a regenerator 42, one line enters a heating coil of the regenerator 42 to heat and regenerate the adsorbent (the temperature of the heat regeneration is 375 ℃ C.; the space velocity is 800 h) -1 ) The gas enters a circulation heating line to heat after exiting the heating coil, and then enters the heating coil again to be recycled; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying regenerated gas containing high-concentration sulfur dioxide into a primary converter 21 to repeatedly recover sulfur;
the regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
3. The obtained effect is as follows:
during 40h from system start-up to operation, SO in the gas is purified 2 The concentration is 0mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the SO in the purified gas after 46h of system operation 2 The concentration reaches 3mg/m 3 At this time, the adsorbent was continuously regenerated in the adsorption unit, and the system was maintained for a total of 1000 hours from the start-up. During the above operation, the loss of the adsorbent was 0.77wt% (note: loss of adsorbent (wt%) = (1-weight of adsorbent after a certain period of use/initial loading weight of adsorbent) ×100%).
The treatment system for the gas containing the hydrogen sulfide provided by the utility model fully utilizes the existing conditions of a sulfur device, and adopts the movable adsorption bed to carry out SO on the incineration tail gas 2 Adsorption, namely, SO is carried out on flue gas of a sulfur device 2 The discharge concentration is reduced to less than or equal to 10mg/m 3 Realizing near zero emission. The system can reasonably adjust the regeneration period of the adsorbent through the content of sulfur dioxide in the purified gas, the adsorbent regeneration process can be continuously carried out or intermittently carried out, and the system can be flexibly controlled according to the adsorption effect and the actual situation, so that the energy consumption increase and the adsorbent abrasion consumption caused by long-term continuous regeneration are avoided. The system adopts the hydrogen-containing hydrogen sulfide removal tail gas from the absorption tower as a regeneration air source of the adsorbent, fully utilizes a heat source in the system to heat the regeneration air source, effectively reduces the regeneration energy consumption, can effectively reduce the use loss of the adsorbent, and is beneficial to long-period stability of the systemAnd (5) fixedly operating. The system can realize the closed cycle of sulfur in the process of treating the gas containing hydrogen sulfide, and the regenerated gas containing sulfur dioxide can return to the sulfur recovery device to continuously recover sulfur resources, so that the total sulfur recovery rate of the system is close to 100%.
In addition, the treatment system for the gas containing the hydrogen sulfide provided by the utility model not only can realize the device flue gas SO during the normal operation of the sulfur device 2 Near zero emission, and can also realize the SO of the device smoke during the shutdown period of the device 2 And (5) discharging after reaching the standard. For the shutdown stage of the device, the regenerated gas cannot be recycled, three bed layers in the movable adsorption bed can be used for treating the regenerated gas, the regenerated gas sequentially passes through the unloading layer, the adsorption layer and the storage layer from bottom to top, the normal adsorption process is carried out, and the storage capacity of the adsorbent in the movable adsorption bed can ensure SO 2 Is free from regeneration and realizes SO 2 And (5) discharging after reaching the standard.
The preferred embodiments of the present utility model have been described in detail above, but the present utility model is not limited thereto. Within the scope of the technical idea of the utility model, a number of simple variants of the technical solution of the utility model are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the utility model, all falling within the scope of protection of the utility model.
Claims (10)
1. A treatment system for a gas containing hydrogen sulfide, which is characterized by comprising a thermal reaction unit (1), a catalytic reaction unit (2), a tail gas purification unit (3) and an adsorption unit (4) which are connected in sequence;
wherein the thermal reaction unit (1) is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
the catalytic reaction unit (2) is used for carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
the tail gas purifying unit (3) is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the Claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two parts of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
the adsorption unit (4) comprises a movable adsorption bed (41) which is connected and loaded with an adsorbent, a regenerator (42) and a lifting device (43), and is used for carrying out adsorption sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
wherein the movable adsorption bed (41) comprises a storage layer (411), an adsorption layer (412) and a discharge layer (413) which are sequentially arranged from top to bottom;
the regenerated adsorbent is circulated back to the moving adsorption bed (41), and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit (1), the catalytic reaction unit (2) and the tail gas purification unit (3).
2. The system according to claim 1, wherein the thermal reaction unit (1) comprises a sulfur producer (11) and a first cooling device (12) connected in sequence.
3. The system according to claim 2, wherein the catalytic reaction unit (2) comprises a primary converter (21) and a secondary converter (22) connected in sequence; wherein the primary converter (21) is connected to the first cooling device (12).
4. A system according to claim 3, wherein the catalytic reaction unit (2) further comprises second (23) and third (24) cooling means; wherein the second cooling device (23) is respectively connected with the primary converter (21) and the secondary converter (22); the third cooling device (24) is connected to the secondary converter (22).
5. The system according to claim 4, wherein the tail gas purification unit (3) comprises a hydrogenation unit (31), an absorption tower (34) and an incinerator (35) connected in sequence; wherein the hydrogenation unit (31) is connected to the third cooling unit (24).
6. The system according to claim 5, wherein the tail gas purification unit (3) further comprises a quench tower (33), the quench tower (33) being connected to the hydrogenation unit (31) and the absorption tower (34), respectively.
7. The system according to claim 5, wherein the adsorption unit (4) further comprises a waste heat boiler (44), a first heat exchanger (45) and a second heat exchanger (46) connected in sequence; wherein,,
the waste heat boiler (44) is connected with the incinerator (35);
the first heat exchanger (45) is respectively connected with the absorption tower (34) and the regenerator (42);
the second heat exchanger (46) is connected with the movable adsorption bed (41).
8. The system according to claim 7, wherein in the moving adsorbent bed (41), the reservoir (411) is connected to the regenerator (42) by a lifting device (43);
the adsorption layer (412) is connected to the second heat exchanger (46);
the discharge layer (413) is connected to the regenerator (42).
9. The system according to claim 7 or 8, wherein the adsorption unit (4) further comprises an auxiliary heater (47), the auxiliary heater (47) being connected to the regenerator (42) and the first heat exchanger (45), respectively.
10. The system of claim 9, wherein the regenerator (42) is connected to at least one of the sulfur producer (11), primary converter (21), secondary converter (22), and hydrogenation unit (31).
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