CN115215301B - Shutdown sulfur blowing method for sulfur recovery device - Google Patents
Shutdown sulfur blowing method for sulfur recovery device Download PDFInfo
- Publication number
- CN115215301B CN115215301B CN202110425212.4A CN202110425212A CN115215301B CN 115215301 B CN115215301 B CN 115215301B CN 202110425212 A CN202110425212 A CN 202110425212A CN 115215301 B CN115215301 B CN 115215301B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- tower
- regeneration
- gas
- unit
- 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
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 281
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 239000011593 sulfur Substances 0.000 title claims abstract description 277
- 238000000034 method Methods 0.000 title claims abstract description 101
- 238000007664 blowing Methods 0.000 title claims abstract description 94
- 238000011084 recovery Methods 0.000 title claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 195
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 144
- 230000008929 regeneration Effects 0.000 claims abstract description 102
- 238000011069 regeneration method Methods 0.000 claims abstract description 102
- 239000007788 liquid Substances 0.000 claims abstract description 96
- 238000010521 absorption reaction Methods 0.000 claims abstract description 88
- 239000003345 natural gas Substances 0.000 claims abstract description 72
- 150000001412 amines Chemical class 0.000 claims abstract description 69
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000010926 purge Methods 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 238000002485 combustion reaction Methods 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010791 quenching Methods 0.000 claims description 44
- 230000000171 quenching effect Effects 0.000 claims description 44
- 239000002918 waste heat Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 239000003546 flue gas Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
- C01B17/0417—Combustion reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
- C01B17/0421—Multistage combustion
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
A method for blowing sulfur by shutdown of a sulfur recovery device comprises the following steps: (1) After the acid gas amount in the sulfur producing furnace is reduced, natural gas is introduced into the sulfur producing furnace for blending combustion, air distribution is adjusted to enable the natural gas to be in secondary equivalent combustion, and steam and nitrogen are supplemented into the sulfur producing furnace; (2) The sulfur production unit purging tail gas enters a hydrogenation unit to generate hydrogenation unit purging tail gas; (3) The tail gas purged by the hydrogenation unit enters an absorption regeneration unit to remove H 2 The purified tail gas after S is discharged to an incinerator for incineration and then discharged; (4) Absorption of H 2 The rich amine liquid after S enters a regeneration tower to regenerate amine liquid; the regenerated acid gas at the top of the regeneration tower returns to the sulfur-making furnace for recycling; (5) After 36-48 hours of sulfur blowing, the regeneration tower is gradually changed into a cold amine circulation, and the residual acid gas is enriched in the amine liquid until the regeneration acid gas is not generated at the top of the regeneration tower. The method is not limited by a single set or a plurality of sets of sulfur recovery devices in a workshop, and has simple operation, no secondary pollution and SO 2 The emission reduction is obvious.
Description
Technical Field
The invention belongs to the technical field of sulfur recovery, and relates to a shutdown sulfur blowing method of a sulfur recovery device, which is suitable for shutdown sulfur blowing processes of the sulfur recovery device adopting a Claus+reduction absorption process in petroleum refining, coal chemical industry, natural gas purification industry and the like.
Background
At present, a Claus+ reduction absorption process is mainly adopted in a domestic and foreign sulfur recovery device. In the process, the acid gas is firstly burnt in a burning furnace at high temperature, wherein hydrocarbons and NH 3 Is completely oxidatively decomposed, and H 2 S is incompletely combusted, about 60-65% is directly converted to elemental sulfur, and then a low temperature Claus reaction occurs via two or three stage catalytic conversion, H in the Claus tail gas 2 S and SO 2 And returning the S which is not trapped after hydrogenation reduction to a sulfur production unit for treatment through an amine liquid system, and discharging purified gas after burning the purified gas in an incinerator, wherein the sulfur recovery rate is more than 99.8%.
In recent years, environmental protection standards in China are increasingly strict, and emission standards for pollutants in petroleum refining industry GB31570-2015 published in 2015 prescribe that sulfur recovery device flue gas SO 2 Emission concentration limits generally require less than 400mg/m 3 The requirement of the key area is less than 100mg/m 3 . Because the concentration of the acid gas is lower during the shutdown, the sulfur producer cannot keep stable flame, and the traditional sulfur recovery device adopts the Claus tail gas to directly go to the incinerator through the overline during the shutdown period, and the method SO 2 The discharge amount often exceeds 30000mg/m 3 The other method adopts gas combustion supporting, the air distribution of the method is greatly influenced by factors such as composition change, and the like, and is easy to cause forced shutdown such as deactivation of catalyst caused by carbon deposition or peroxidation, increase of bed pressure drop and the like, so that the development of a shutdown method of a sulfur recovery device is urgent to solve the problems.
CN103566730a discloses a method for treating sulfur removal purge tail gas generated in the shutdown process of a sulfur recovery device, which uses sulfur dioxide generated by completely combusting raw acid gas to purge a claus unit, sends the sulfur removal purge tail gas into a tail gas system for treatment, and controls hydrogenation reduction conditions to realize reduction of sulfur dioxide concentration in discharged flue gas. According to the method, excessive air is required to be injected into the sulfur production furnace for completely combusting the raw acid gas, once the condition of peroxy occurs in the sulfur blowing operation process, the system is extremely easy to fly to the temperature, amine liquid is easy to degrade, the burden of an absorption and regeneration system is increased, and in addition, the tail gas in the later stage of sulfur removal cannot be well treated.
CN206447572U discloses a sulfur recovery device with hot nitrogen purging, which is characterized in that a sulfur-making combustion furnace, a waste heat boiler and a primary sulfur condenser are sequentially connected, a secondary sulfur condenser is arranged between the primary reactor and the secondary reactor, a tertiary sulfur condenser is arranged at the outlet of the secondary reactor, the liquid sulfur outlets of the primary sulfur condenser, the secondary sulfur condenser and the tertiary sulfur condenser are connected with a liquid sulfur pool, the gas outlet of the tertiary sulfur condenser is connected with a tail gas treatment device, nitrogen is heated by a nitrogen heater and then is connected with the waste heat boiler outlet, the inlets of the primary reactor and the secondary reactor, and a hot air purging pipeline is arranged at the inlet of the primary reactor and/or the inlet of the secondary reactor. The device consumes nitrogen greatly and needs to increase nitrogen heating facilities, increases device energy consumption, and in addition, the device is only suitable for shutdown of two or more sulfur devices when the device is stopped and the raw acid gas is required to be cut off.
CN105819404a discloses a zero-emission shutdown process for sulfur recovery device, which comprises introducing shutdown tail gas from the quenching tower to the incinerator for incineration, and absorbing SO by the alkali liquor absorption tower 2 The method belongs to the post-alkaline washing technology, has high construction and operation costs and serious corrosion, and simultaneously generates waste alkali liquor to form new pollution.
In order to solve the technical problems, the invention provides a shutdown sulfur blowing method of a sulfur recovery device.
Disclosure of Invention
The invention aims to provide a method for blowing sulfur by stopping a sulfur recovery device, which can be solvedBlowing tail gas of sulfur production unit during stop and stop sulfur blowing process directly goes to incinerator through overline SO as to influence flue gas SO 2 The problem of emission is not limited by a single set or a plurality of sets of sulfur recovery devices in a workshop, the operation is simple, the applicability is strong, the sulfur recovery device in the whole shutdown sulfur blowing process reaches the standard and emits, and the method is widely applied to the shutdown sulfur blowing process of the sulfur recovery device adopting the Claus+ reduction absorption process in industries such as petroleum refining, natural gas purification, coal chemical industry and the like.
The invention provides a shutdown sulfur blowing method of a sulfur recovery device, which comprises a sulfur making unit, a hydrogenation unit, an absorption regeneration unit, an incinerator and a chimney which are sequentially connected, wherein the sulfur making unit comprises a sulfur making furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor, a tertiary condenser and a tail gas liquid separating tank, the hydrogenation unit comprises a tail gas heater, a hydrogenation reactor, a steam generator and a quenching tower, and the absorption regeneration unit comprises an absorption tower and a regeneration tower;
wherein the method comprises the following steps:
(1) After the acid gas amount in the sulfur making furnace is reduced and the reaction temperature in the sulfur making furnace of the sulfur making unit is difficult to maintain at the first temperature, natural gas is introduced into the sulfur making furnace for blending combustion, air distribution is adjusted to enable natural gas to be in secondary equivalent combustion, steam and nitrogen are supplemented into the sulfur making furnace, so that carbon precipitation and peroxy of a system are avoided while the reaction temperature in the sulfur making furnace is maintained at the first temperature, and tail gas generated by blowing the sulfur making unit of the sulfur making unit can sequentially enter a hydrogenation unit and an absorption regeneration unit without going through a cross line to the incinerator;
(2) The tail gas from the sulfur producing unit is purged into a hydrogenation unit, wherein the tail gas is not H 2 Hydrogenation of S-containing compounds to H 2 S, get H-containing 2 S, purging tail gas by a hydrogenation unit;
(3) The tail gas purged by the hydrogenation unit enters an absorption tower of an absorption regeneration unit, wherein H in the tail gas purged by the hydrogenation unit 2 S is absorbed by lean amine liquid in the absorption tower to remove H 2 The purified tail gas after S is discharged to an incinerator for incineration through the top of the absorption tower and then discharged;
(4) H is absorbed in the absorption tower 2 The rich amine liquid after S enters a regeneration tower to regenerate amine liquid; the regenerated acid gas at the top of the regeneration tower returns to the sulfur-making furnace for recycling and reuse as an acid gas source of a sulfur-making unit;
(5) After 36-48 hours of sulfur blowing, the regeneration tower is gradually changed into cold amine circulation, and the residual acid gas is enriched in the amine liquid until no regenerated acid gas is generated at the top of the regeneration tower, so that no acid gas is sent to other sulfur recovery devices during the whole shutdown sulfur blowing period.
Wherein, sulfur making unit include: the device comprises a sulfur making furnace, a waste heat boiler, a first-stage condenser, a first-stage heater, a first-stage reactor, a second-stage condenser, a second-stage heater, a second-stage reactor, a third-stage condenser, a tail gas liquid separating tank, pipelines for connecting the devices, a delivery pump, a valve and an instrument device for self control, wherein the delivery pump, the valve and the instrument device are arranged on the connecting pipelines. Wherein, the hearth temperature of the sulfur producing furnace is 1100-1350 ℃, the inlet temperature of the primary reactor is 220-250 ℃, and the inlet temperature of the secondary reactor is 210-240 ℃.
Wherein, the hydrogenation unit includes: the tail gas heater, the hydrogenation reactor, the steam generator, the quenching tower, the pipelines for connecting the devices, the delivery pump, the valve and the instrument device for automatic control are sequentially connected. Wherein the inlet temperature of the hydrogenation reactor is 250-300 ℃.
Wherein the absorption regeneration unit comprises: the device comprises an absorption tower, a regeneration tower, pipelines for connecting the devices, a delivery pump, a valve and an instrument device for automatic control, wherein the delivery pump, the valve and the instrument device are arranged on the connecting pipelines, the liquid phase outlet of the absorption tower is connected with the liquid phase inlet of the regeneration tower through a pipeline, and the liquid phase outlet of the regeneration tower is connected with the liquid phase inlet of the absorption tower through a pipeline.
The tail gas purging unit is used for purging the tail gas from the outlet of the tail gas liquid separating tank.
The hydrogenation unit purging tail gas refers to purging tail gas at the outlet of the top of the quenching tower.
Wherein the purified tail gas means that H is removed from tail gas purged by a hydrogenation unit in an absorption tower 2 Absorption after SAnd (5) ejecting out the gas from the tower.
Wherein in the step (1), the first temperature is 1100-1350 ℃.
Wherein in the step (1), the amount of the air fed into the furnace is adjusted according to the amount of the natural gas fed into the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air required by each cubic meter of natural gas is controlled to be 8-9.5m 3 Preferably 8.5-9m 3 。
Wherein in the step (1), steam is added into the sulfur producing furnace according to the amount of the natural gas fed into the furnace, and the steam is added according to the amount of 1m 3 The natural gas/h is mixed with 1.9-2.3kg/h steam, preferably 1.9-2.1kg/h steam.
In the step (1), because the natural gas has a large combustion heat value, the temperature of the sulfur producing furnace may be slightly high, nitrogen is required to be fed into the sulfur producing furnace according to the temperature of the sulfur producing furnace (controlled at 1100-1350 ℃) in the sulfur blowing process, the sulfur carrying capacity and the heat carrying capacity of the sulfur producing system are increased, and the local overtemperature of equipment is avoided, wherein the flow of the nitrogen fed with the nitrogen is calculated according to the formula (1):
Q＝0.2746n 3 -9.0138n 2 +131.28n-26.718 (1)
wherein Q is the flow rate (m) 3 ) N is the scale of the plant (ten thousand tons/year).
Wherein in the step (2), S and SO in the tail gas are purged by the sulfur producing unit 2 In the hydrogenation unit, under the action of catalyst in hydrogenation reactor, reduced to produce H 2 S, the reaction process is shown in formulas (2) - (3):
S x +xH 2 →xH 2 S (2)
SO 2 +3H 2 →H 2 S+2H 2 O (3)
wherein in the step (2), the sulfur producing unit sweeps SO in the tail gas 2 S is hydrogenated in a hydrogenation reactor to generate H-containing gas 2 S gas is cooled by a steam generator and a quenching tower and then is discharged from an outlet of the quenching tower as a tail gas purged by a hydrogenation unit.
Wherein, a hydrogen online analyzer is arranged at the air outlet of the quenching tower, and the hydrogen content in the purging tail gas of the hydrogenation unit at the outlet of the quenching tower is controlled to be more than 1vol percent, preferably 2-4vol percent.
Wherein, the pH value of the quenching tower is controlled to 7-9, and alkali injection measures are adopted if necessary.
In the step (3), the tail gas purged by the hydrogenation unit enters the lower part of the absorption tower and is in countercurrent contact with lean amine liquid in the absorption tower to absorb H 2 S, the purified tail gas at the top of the absorption tower is discharged to the incinerator for incineration, and the temperature of the top of the absorption tower is controlled at 25-40 ℃, preferably 25-38 ℃.
Wherein in the step (4), H is absorbed in the absorption tower 2 And (3) discharging the rich amine liquid after S through the bottom of the absorption tower, entering the upper part of the regeneration tower for regeneration, and returning the lean amine liquid obtained by regeneration to the upper part of the absorption tower through the bottom of the regeneration tower.
In the step (4), the regenerated acid gas returns to the sulfur producing furnace from the top of the regeneration tower to be recycled and reused as the acid gas source of the sulfur producing unit, and the sulfur producing unit can continuously produce sulfur, thereby effectively utilizing sulfur resources during sulfur blowing.
In the step (4), a reboiler at the bottom of the regeneration tower provides a heat source for the regeneration of the rich amine liquid, the temperature of the top of the regeneration tower is controlled to be 100-115 ℃, the temperature of the bottom of the tower is controlled to be 115-120 ℃, and the pressure of the top of the tower is controlled to be 0.06-0.10Mpa.
Wherein the regenerated acid gas specifically refers to high-concentration H-containing gas extracted from the rich amine liquid 2 S gas, wherein the high concentration means a concentration of 50 to 95 vol%.
In the step (5), after 36-48 hours of sulfur blowing, reducing the steam amount of a reboiler at the bottom of the regeneration tower at a rate of 3-4 tons per hour, gradually reducing the temperature of the regeneration tower to 25-38 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the regeneration tower, pumping the amine liquid in the absorption tower into the regeneration tower through a tower bottom pump after the enrichment is finished, and leading the amine liquid to an amine liquid storage tank.
The invention has the following beneficial technical effects:
(1) The method of the invention can ensure the normal operation of the sulfur producing unit, the hydrogenation unit and the absorption regeneration unit during the shutdown and sulfur blowing of the sulfur recovery device, and can solve the problem that the tail gas purged by the sulfur producing unit during the shutdown and sulfur blowing of the sulfur recovery device is directly sent to the incinerator for producing through the overlineFlue gas SO 2 The problem of exceeding discharge standard is particularly suitable for the shutdown process of a single sulfur recovery device, is not limited by a single sulfur recovery device or a plurality of sulfur recovery devices in a workshop, and has the advantages of standard discharge of the sulfur recovery device in the whole shutdown process, simple operation, no secondary pollution and SO 2 The emission reduction is obvious.
(2) In the step (1) of the method, natural gas is introduced into the sulfur producing furnace for blending combustion, air distribution is adjusted to enable the natural gas to be in equivalent combustion, steam and nitrogen are supplemented into the sulfur producing furnace, so that carbon precipitation and peroxy of a system are avoided while the reaction temperature in the sulfur producing furnace is maintained at a first temperature, a hydrogenation unit and an absorption regeneration unit are protected, and purge tail gas generated by the sulfur producing unit can sequentially enter the hydrogenation unit and the absorption regeneration unit without going through a cross line to the incinerator. The specific reason is that:
the blowing process of the sulfur producing unit in the traditional shutdown sulfur blowing period of the sulfur recovery device has large air distribution deviation, has obvious influence on the hydrogenation unit catalyst and the amine liquid of the absorption regeneration unit, and needs to cut the hydrogenation unit and the absorption regeneration unit out of the sulfur blowing system in the sulfur blowing period.
In the method of the invention:
(i) By controlling the secondary equivalent combustion of natural gas, the degradation loss of amine liquid caused by system peroxidation can be prevented, the quality of the amine liquid of the absorption and regeneration unit is ensured, and the absorption and regeneration unit operates normally during the shutdown and sulfur blowing period of the sulfur recovery device.
(ii) By injecting steam into the sulfur producing furnace, the sulfur producing furnace reacts with CO, C and the like generated by incomplete combustion of natural gas to avoid carbon precipitation of the catalyst, and a certain amount of H can be provided for a hydrogenation reactor 2 The reaction process is shown in the formulas (4) - (5), so that the reduction environment of the hydrogenation system can be further ensured, and the hydrogenation unit can normally operate during the shutdown and sulfur blowing of the sulfur recovery device. Therefore, the hydrogenation unit and the absorption regeneration unit are not required to be cut out of the sulfur blowing system during sulfur blowing, and the flue gas SO caused by the fact that the purging tail gas generated by the sulfur making unit goes to the incinerator through the overline is avoided 2 And the emission exceeds the standard.
H 2 O+C→CO+H 2 (4)
H 2 O+CO→CO 2 +H 2 (5)
(3) According to the method, during the whole shutdown sulfur blowing period, the acid gas of the upstream device is not required to be cut off, the regenerated acid gas generated by the device is returned to the sulfur production furnace for recycling as the acid gas source of the sulfur production unit in the early stage, and is enriched into the amine liquid in the later stage, and the acid gas is not required to be sent to a non-shutdown sulfur recovery device for treatment.
(4) The shutdown sulfur blowing method is not only limited to a sulfur recovery device adopting medium-pressure steam heat exchange, but also applicable to sulfur recovery devices adopting gas-gas heat exchange, high-temperature blending, electric heating, heating furnaces and other processes.
(5) The shutdown sulfur blowing method can lead the flue gas SO during the shutdown sulfur blowing period of the whole sulfur device 2 The discharge is less than 100mg/m 3 Realizing the standard discharge in the shutdown process.
Brief description of the drawings
FIG. l is a flow chart of a shutdown sulfur blowing method of the sulfur recovery device.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
FIG. 1 shows a flow chart of a shutdown sulfur blowing method of the sulfur recovery apparatus of the present invention. Wherein each reference numeral means: 1. an air inlet; 2. an acid gas inlet; 3. a natural gas inlet; 4. a steam inlet; 5. a nitrogen inlet; 6. a sulfur producing furnace; 7. a waste heat boiler; 8. a first-stage condenser; 9. a primary heater; 10. a first stage reactor; 11. a second-stage condenser; 12. a secondary heater; 13. a secondary reactor; 14. a three-stage condenser; 15. a tail gas separating tank; 16. a tail gas heater; 17. a hydrogenation reactor; 18. a steam generator; 19. a quenching tower; 20. a circulating water pump; 21. a circulating water cooler; 22. an absorption tower; 23. a rich liquid pump; 24. a lean rich liquid heat exchanger; 25. a regeneration tower; 26. a regenerator at the bottom of the regeneration column; 27. an amine liquid storage tank; 28. a lean liquid pump; 29. a liquid sulfur pool; 30. an incinerator; 31. cigarette with smokeChimney; h. H 2 S/SO 2 A ratio analyzer; 33. hydrogen on-line analyzer.
The method for blowing sulfur out of the sulfur recovery apparatus according to the present invention is specifically described below with reference to fig. 1, and includes:
(i) When the sulfur production unit is stopped, after the acid gas quantity generated by an upstream device is reduced, a natural gas inlet (3) is opened, and the gas flow rate of the mixed combustion natural gas is gradually increased to maintain the furnace temperature of the sulfur production furnace;
the air quantity entering the air inlet (1) is adjusted according to the natural gas quantity entering the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air is 8-9.5m for each cubic meter of natural gas 3 Preferably 8.5-9m 3 ；
The natural gas inlet (3) is opened and the steam inlet (4) is opened simultaneously, steam is supplemented into the sulfur producing furnace according to the amount of the natural gas fed into the furnace according to the ratio of 1m 3 1.9-2.3kg/h steam, preferably 1.9-2.1kg/h steam, are mixed with the natural gas/h;
simultaneously opening a nitrogen inlet (5) in the sulfur blowing process, adjusting the flow of nitrogen fed into the furnace according to the formula (1), and controlling the temperature of a sulfur producing furnace (6) to be 1100-1350 ℃;
the sulfur blowing process gas generated by a sulfur producing furnace (6) in a sulfur producing unit sequentially enters a waste heat boiler (7), a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15); controlling the inlet temperature of the primary reactor to be 220-250 ℃ and the inlet temperature of the secondary reactor to be 210-240 ℃;
sulfur generated in the sulfur blowing process is condensed by a first-stage condenser, a second-stage condenser and a third-stage condenser and then enters a liquid sulfur pool (29), and tail gas is discharged from an outlet of a tail gas liquid separating tank (15) to a sulfur making unit for blowing tail gas;
(ii) In the hydrogenation unit, the tail gas purged by the sulfur making unit sequentially enters a tail gas heater (16), a hydrogenation reactor (17), a steam generator (18) and a quenching tower (19);
controlling the inlet temperature of the hydrogenation reactor to be 250-300 ℃ and controlling the hydrogen content at the outlet of the quenching tower to be more than 1vol%, preferably 2-4vol%; observing pH value change of the quenching tower at any time in the sulfur blowing process, controlling the pH value of the quenching tower to be 7-9, and taking alkali injection measures if necessary;
s and SO in tail gas purged from sulfur producing unit 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), and discharging hydrogenation unit purging tail gas from the top of the quenching tower (19);
(iii) In the absorption regeneration unit, the tail gas purged by the hydrogenation unit enters the lower part of the absorption tower (22) and is in countercurrent contact with lean amine liquid in the absorption tower (22) to absorb H 2 S, the purified tail gas at the top of the tower is absorbed and then enters a tail gas incinerator (30) for incineration and is discharged; wherein the temperature of the top of the absorption tower is controlled to be 25-40 ℃, preferably 25-38 ℃;
(iv) The rich amine liquid at the bottom of the absorption tower (22) enters the upper part of a regeneration tower to be regenerated, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the top of the regeneration tower returns to the sulfur-making furnace to be recycled and reused as an acid gas source of the sulfur-making unit;
wherein, the temperature of the top of the regeneration tower is controlled to be 100-115 ℃, the temperature of the bottom of the tower is controlled to be 115-120 ℃, and the pressure of the top of the tower is controlled to be 0.06-0.10Mpa;
(v) After 36-48 hours of sulfur blowing, reducing the steam amount of a reboiler (26) at the bottom of the regeneration tower at a rate of 3-4 tons per hour, gradually reducing the temperature of the regeneration tower to 25-38 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the regeneration tower, pumping the amine liquid in the absorption tower into the regeneration tower through a tower bottom rich liquid pump (23) after the enrichment is finished, and introducing the amine liquid into an amine liquid storage tank (27).
Example 1
The sulfur blowing method comprises the following steps of: after the acid gas amount generated by the upstream device is reduced, a natural gas inlet (3) is opened, the mixed combustion natural gas flow is gradually increased to maintain the furnace temperature, and the air amount of an air inlet (1) is adjusted according to the natural gas amount to enable natural gas and air to be combusted according to the equivalent weight, wherein 9m of air is needed for each cubic meter of natural gas 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur producing furnace according to the amount of the natural gas fed into the furnace by 1m 3 1.9kg/h steam is matched with the/h natural gas, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow of nitrogen entering the furnace is adjusted to 650m 3 And/h, controlling the temperature of the sulfur producing furnace (6) to 1200 ℃. The sulfur blowing process gas generated by the sulfur producing furnace (6) in the sulfur producing unit sequentially enters the waste heat boiler(7) The method comprises the steps of a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15), wherein the inlet temperature of the primary reactor is 233 ℃, the inlet temperature of the secondary reactor is 213 ℃, sulfur generated in the sulfur blowing process is condensed by the primary condenser, the secondary condenser and the tertiary condenser and then enters a liquid sulfur tank (29), sulfur making unit purging tail gas at the outlet of the tail gas liquid separating tank (15) sequentially enters the tail gas heater (16), a hydrogenation reactor (17), a steam generator (18) and a quenching tower (19), the inlet temperature of the hydrogenation reactor is 256 ℃, the hydrogen content at the outlet of the quenching tower is controlled to be 3vol%, and S and SO in the sulfur making unit purging tail gas are sequentially introduced into the tail gas 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), introducing the hydrogenated and reduced purging tail gas into the lower part of an absorption tower (22), and countercurrent contacting with lean amine liquid in the absorption tower (22) to absorb H 2 S, the tail gas purified from the tower top enters a tail gas incinerator (30) for incineration and then is discharged, the rich amine liquid at the bottom of the absorption tower (22) enters the upper part of the regeneration tower for regeneration, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the tower top returns to the sulfur making furnace for recycling and recycling as an acid gas source of a sulfur making unit. The pH value change of the quenching tower is observed at any time in the sulfur blowing process, the pH value of the quenching tower is controlled at 8, alkali injection measures are adopted when necessary, the temperature of the absorption tower top is 30 ℃, the temperature of the regeneration tower top is 107 ℃, the temperature of the tower bottom is 118 ℃, and the pressure of the tower top is 0.08Mpa. After 37 hours of sulfur blowing, the steam amount of a reboiler (26) at the bottom of the regeneration tower is reduced at a rate of 3 tons per hour, the temperature of the regeneration tower is gradually reduced to 30 ℃, the residual acid gas is enriched in the amine liquid until no regenerated acid gas is generated at the top of the tower, and the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom rich liquid pump (23) and then is led to an amine liquid storage tank (27) after the enrichment is finished.
Compared with the traditional shutdown method, the method of the embodiment 1 solves the problems of exceeding standard emission caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like 2 The discharge is less than 80mg/m 3 Meets the latest environmental protection requirement.
Comparative example 1
When a 10 ten thousand ton/year sulfur recovery device is shut down, a traditional shutdown sulfur blowing method is adoptedI.e. the flue gas SO from the cross-line burning of the Claus tail gas in the incinerator 2 The discharge is 20000mg/m 3 Left and right.
Example 2
The sulfur blowing method is as follows: after the acid gas amount generated by the upstream device is reduced, a natural gas inlet (3) is opened, the mixed combustion natural gas flow is gradually increased to maintain the furnace temperature, and the air amount of an air inlet (1) is adjusted according to the natural gas amount to enable natural gas and air to be combusted according to the equivalent weight, wherein the air requirement is 8.5m for each cubic meter of natural gas 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur producing furnace according to the amount of the natural gas fed into the furnace by 1m 3 2.05kg/h steam is matched with the/h natural gas, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow of nitrogen entering the furnace is adjusted to 590m 3 And/h, controlling the temperature of the sulfur producing furnace (6) to 1190 ℃. The method comprises the steps that sulfur blowing process gas generated by a sulfur producer (6) in a sulfur production unit sequentially enters a waste heat boiler (7), a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15), the inlet temperature of the primary reactor is 240 ℃, the inlet temperature of the secondary reactor is 220 ℃, sulfur generated in the sulfur blowing process is condensed by the primary condenser, the secondary condenser and the tertiary condenser and then enters a liquid sulfur tank (29), sulfur production unit purging tail gas at the outlet of the tail gas liquid separating tank (15) sequentially enters a tail gas heater (16), a hydrogenation reactor (17), a steam generator (18), a quenching tower (19), the inlet temperature of the hydrogenation reactor is 260 ℃, the hydrogen content at the outlet of the quenching tower is controlled at 4vol%, and S and SO in the sulfur production unit purging tail gas are sequentially introduced into the tail gas heater (16) 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), introducing the hydrogenated and reduced purging tail gas into the lower part of an absorption tower (22), and countercurrent contacting with lean amine liquid in the absorption tower (22) to absorb H 2 S, the tail gas purified from the tower top enters a tail gas incinerator (30) for incineration and then is discharged, the rich amine liquid at the bottom of the absorption tower (22) enters the upper part of the regeneration tower for regeneration, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the tower top returns to the sulfur making furnace for recycling and recycling as an acid gas source of a sulfur making unit. Observing pH value change of the quenching tower in time in the sulfur blowing process, and controlling the pH value of the quenching tower at9, if necessary, adopting alkali injection measures, wherein the temperature of the absorption tower top is 28 ℃, the temperature of the regeneration tower top is 105 ℃, the temperature of the tower bottom is 117 ℃, and the pressure of the tower top is 0.082Mpa. After sulfur blowing for 40 hours, the steam amount of a reboiler (26) at the bottom of the regeneration tower is reduced at a rate of 3 tons per hour, the temperature of the regeneration tower is gradually reduced to 28 ℃, the residual acid gas is enriched in the amine liquid until no regenerated acid gas is generated at the top of the tower, and the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom rich liquid pump (23) and then is led to an amine liquid storage tank (27) after the enrichment is finished.
Compared with the traditional shutdown method, the method of the embodiment 2 solves the problems of exceeding standard emission caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like 2 The discharge is less than 60mg/m 3 Meets the latest environmental protection requirement.
Comparative example 2
When a sulfur recovery device is shut down for 8 ten thousand tons/year, a traditional shutdown sulfur blowing method is adopted, namely, the Claus tail gas is subjected to overline to the flue gas SO after the burning of an incinerator 2 The discharge is 24000mg/m 3 Left and right.
Example 3
The sulfur blowing method is as follows: after the acid gas amount generated by the upstream device is reduced, a natural gas inlet (3) is opened, the mixed combustion natural gas flow is gradually increased to maintain the furnace temperature, and the air amount of an air inlet (1) is adjusted according to the natural gas amount to enable natural gas and air to be combusted according to the equivalent weight, wherein the air requirement of each cubic meter of natural gas is 8.8m 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur producing furnace according to the amount of the natural gas fed into the furnace by 1m 3 2kg/h steam is matched with the/h natural gas, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow of nitrogen entering the furnace is adjusted to 720m 3 And/h, controlling the temperature of the sulfur producing furnace (6) to 1220 ℃. The sulfur blowing process gas generated by a sulfur making furnace (6) in a sulfur making unit sequentially enters a waste heat boiler (7), a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15), the inlet temperature of the primary reactor is 236 ℃, the inlet temperature of the secondary reactor is 215 ℃, and sulfur generated in the sulfur blowing process passes through the primary and the secondaryThe condensed liquid sulfur pool (29) is entered after the condensation of the stage condenser and the three stage condenser, the sulfur making unit sweeping tail gas at the outlet of the tail gas separating tank (15) sequentially enters the tail gas heater (16), the hydrogenation reactor (17), the steam generator (18) and the quenching tower (19), the inlet temperature of the hydrogenation reactor is 251 ℃, the hydrogen content at the outlet of the quenching tower is controlled at 2.5vol%, and S and SO in the sulfur making unit sweeping tail gas are controlled 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), introducing the hydrogenated and reduced purging tail gas into the lower part of an absorption tower (22), and countercurrent contacting with lean amine liquid in the absorption tower (22) to absorb H 2 S, the tail gas purified from the tower top enters a tail gas incinerator (30) for incineration and then is discharged, the rich amine liquid at the bottom of the absorption tower (22) enters the upper part of the regeneration tower for regeneration, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the tower top returns to the sulfur making furnace for recycling and recycling as an acid gas source of a sulfur making unit. The pH value change of the quenching tower is observed at any time in the sulfur blowing process, the pH value of the quenching tower is controlled at 7, alkali injection measures are adopted when necessary, the temperature of the absorption tower top is 29 ℃, the temperature of the regeneration tower top is 109 ℃, the temperature of the tower bottom is 119 ℃, and the pressure of the tower top is 0.079Mpa. After 39 hours of sulfur blowing, the steam amount of a reboiler (26) at the bottom of the regeneration tower is reduced at a rate of 3.2 tons per hour, the temperature of the regeneration tower is gradually reduced to 29 ℃, the rest acid gas is enriched in the amine liquid until no regenerated acid gas is generated at the top of the tower, and the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom enrichment pump (23) and then is led to an amine liquid storage tank (27) after the enrichment is finished.
Compared with the traditional shutdown method, the method solves the problems of exceeding standard emission and the like caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the method is adopted to shutdown flue gas SO in the sulfur blowing stage 2 The discharge is less than 70mg/m 3 Meets the latest environmental protection requirement.
Comparative example 3
When a sulfur recovery device is shut down for 12 ten thousand tons/year, a traditional shutdown sulfur blowing method is adopted, namely, the Claus tail gas is subjected to overline to the flue gas SO after being burnt by an incinerator 2 The discharge is 25000mg/m 3 Left and right.
Example 4
The sulfur blowing method is as follows: after the acid gas amount generated by the upstream device is reduced, the device is openedA natural gas inlet (3) for gradually increasing the flow of the co-fired natural gas to maintain the furnace temperature, and adjusting the air quantity of the air inlet (1) according to the natural gas flow to ensure that the natural gas and the air are combusted according to the equivalent weight, wherein the air requirement is 8.6m for each cubic meter of natural gas 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur producing furnace according to the amount of the natural gas fed into the furnace by 1m 3 2.1kg/h steam is matched with the/h natural gas, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow of nitrogen entering the furnace is regulated to 860m 3 And/h, controlling the temperature of the sulfur producing furnace (6) to be 1235 ℃. The method comprises the steps that sulfur blowing process gas generated by a sulfur making furnace (6) in a sulfur making unit sequentially enters a waste heat boiler (7), a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15), the inlet temperature of the primary reactor is 242 ℃, the inlet temperature of the secondary reactor is 230 ℃, sulfur generated in the sulfur blowing process is condensed by the primary condenser, the secondary condenser and the tertiary condenser and then enters a liquid sulfur tank (29), sulfur making unit purging tail gas at the outlet of the tail gas liquid separating tank (15) sequentially enters a tail gas heater (16), a hydrogenation reactor (17), a steam generator (18), a quenching tower (19), the inlet temperature of the hydrogenation reactor is 255 ℃, the hydrogen content at the outlet of the quenching tower is controlled at 4vol%, and S and SO in the sulfur making unit purging tail gas are sequentially introduced into the tail gas 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), introducing the hydrogenated and reduced purging tail gas into the lower part of an absorption tower (22), and countercurrent contacting with lean amine liquid in the absorption tower (22) to absorb H 2 S, the tail gas purified from the tower top enters a tail gas incinerator (30) for incineration and then is discharged, the rich amine liquid at the bottom of the absorption tower (22) enters the upper part of the regeneration tower for regeneration, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the tower top returns to the sulfur making furnace for recycling and recycling as an acid gas source of a sulfur making unit. The pH value change of the quenching tower is observed at any time in the sulfur blowing process, the pH value of the quenching tower is controlled at 8, alkali injection measures are adopted when necessary, the temperature of the absorption tower top is 28 ℃, the temperature of the regeneration tower top is 103 ℃, the temperature of the tower bottom is 117 ℃, and the pressure of the tower top is 0.07Mpa. After 36 hours of sulfur blowing, the steam level in the reboiler (26) at the bottom of the regeneration tower was reduced at a rate of 3.9 tons per hour, the temperature of the regeneration tower was gradually reduced to 28 ℃, and the remaining acid gas was enriched in the amine liquidAnd (3) until no regenerated acid gas is generated at the top of the tower, after enrichment is finished, pumping the amine liquid in the absorption tower into the regeneration tower through a tower bottom rich liquid pump (23), and then leading the amine liquid to an amine liquid storage tank (27).
Compared with the traditional shutdown method, the method solves the problems of exceeding standard emission and the like caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the method is adopted to shutdown flue gas SO in the sulfur blowing stage 2 The discharge is less than 55mg/m 3 Meets the latest environmental protection requirement.
Comparative example 4
When a 15 ten thousand tons/year sulfur recovery device is shut down, a traditional shutdown sulfur blowing method is adopted, namely, the Claus tail gas is subjected to overline to the flue gas SO after the incineration of the incinerator 2 The discharge is 27000mg/m 3 Left and right.
Example 5
The sulfur blowing method is as follows: after the acid gas amount generated by the upstream device is reduced, a natural gas inlet (3) is opened, the mixed combustion natural gas flow is gradually increased to maintain the furnace temperature, and the air amount of an air inlet (1) is adjusted according to the natural gas amount to enable natural gas and air to be combusted according to the equivalent weight, wherein the air requirement of each cubic meter of natural gas is 8.7m 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur producing furnace according to the amount of the natural gas fed into the furnace by 1m 3 The natural gas/h is matched with 1.95kg/h steam, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow of nitrogen entering the furnace is adjusted to 430m 3 And/h, controlling the temperature of the sulfur producing furnace (6) to 1300 ℃. The method comprises the steps that sulfur blowing process gas generated by a sulfur producer (6) in a sulfur production unit sequentially enters a waste heat boiler (7), a primary condenser (8), a primary heater (9), a primary reactor (10), a secondary condenser (11), a secondary heater (12), a secondary reactor (13), a tertiary condenser (14) and a tail gas liquid separating tank (15), the inlet temperature of the primary reactor is 236 ℃, the inlet temperature of the secondary reactor is 219 ℃, sulfur generated in the sulfur blowing process is condensed by the primary condenser, the secondary condenser and the tertiary condenser and then enters a liquid sulfur tank (29), sulfur production unit purge tail gas at the outlet of the tail gas liquid separating tank (15) sequentially enters a tail gas heater (16), a hydrogenation reactor (17), a steam generator (18), a quenching tower (19), the inlet temperature of the hydrogenation reactor is 259 ℃, the hydrogen content at the outlet of the quenching tower is controlled at 4vol%, and the sulfur production unit purge tail gasS and SO of (2) 2 Reducing under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quenching tower (19), introducing the hydrogenated and reduced purging tail gas into the lower part of an absorption tower (22), and countercurrent contacting with lean amine liquid in the absorption tower (22) to absorb H 2 S, the tail gas purified from the tower top enters a tail gas incinerator (30) for incineration and then is discharged, the rich amine liquid at the bottom of the absorption tower (22) enters the upper part of the regeneration tower for regeneration, the lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the regenerated acid gas at the tower top returns to the sulfur making furnace for recycling and recycling as an acid gas source of a sulfur making unit. The pH value change of the quenching tower is observed at any time in the sulfur blowing process, the pH value of the quenching tower is controlled at 9, alkali injection measures are adopted when necessary, the temperature of the absorption tower top is 26 ℃, the temperature of the regeneration tower top is 108 ℃, the temperature of the tower bottom is 119 ℃, and the pressure of the tower top is 0.081Mpa. After sulfur blowing for 41 hours, the steam amount of a reboiler (26) at the bottom of the regeneration tower is reduced at a rate of 3.5 tons per hour, the temperature of the regeneration tower is gradually reduced to 26 ℃, the rest acid gas is enriched in the amine liquid until no regenerated acid gas is generated at the top of the tower, and the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom enrichment pump (23) and then is led to an amine liquid storage tank (27) after the enrichment is finished.
Compared with the traditional shutdown method, the method solves the problems of exceeding standard emission and the like caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the method is adopted to shutdown flue gas SO in the sulfur blowing stage 2 The discharge is less than 50mg/m 3 Meets the latest environmental protection requirement.
Comparative example 5
When a sulfur recovery device is shut down for a certain 5 ten thousand tons/year, a traditional shutdown sulfur blowing method is adopted, namely, the Claus tail gas is subjected to overline to the flue gas SO after being burnt by an incinerator 2 The discharge was 15000mg/m 3 Left and right.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (7)
1. The device comprises a sulfur making unit, a hydrogenation unit, an absorption and regeneration unit, an incinerator and a chimney which are sequentially connected, wherein the sulfur making unit comprises a sulfur making furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor, a tertiary condenser and a tail gas liquid separating tank, the hydrogenation unit comprises a tail gas heater, a hydrogenation reactor, a steam generator and a quenching tower, and the absorption and regeneration unit comprises an absorption tower and a regeneration tower;
wherein the method comprises the following steps:
(1) After the acid gas amount in the sulfur making furnace is reduced and the reaction temperature in the sulfur making furnace of the sulfur making unit is difficult to maintain at the first temperature, natural gas blending combustion is introduced into the sulfur making furnace, air distribution is adjusted to enable natural gas to be in sub-equivalent combustion, steam and nitrogen are supplemented into the sulfur making furnace, and therefore carbon precipitation and peroxy of a system are avoided while the reaction temperature in the sulfur making furnace is maintained at the first temperature, and blowing tail gas of the sulfur making unit generated by the sulfur making unit can sequentially enter a hydrogenation unit and an absorption regeneration unit without a cross line to remove the incinerator;
(2) The tail gas from the sulfur producing unit is purged into a hydrogenation unit, wherein the tail gas is not H 2 Hydrogenation of S-containing compounds to H 2 S, get H-containing 2 S, purging tail gas by a hydrogenation unit;
(3) The tail gas purged by the hydrogenation unit enters an absorption tower of an absorption regeneration unit, wherein H in the tail gas purged by the hydrogenation unit 2 S is absorbed by lean amine liquid in the absorption tower to remove H 2 The purified tail gas after S is discharged to an incinerator for incineration through the top of the absorption tower and then discharged;
(4) H is absorbed in the absorption tower 2 The rich amine liquid after S enters a regeneration tower to regenerate amine liquid; the regenerated acid gas at the top of the regeneration tower returns to the sulfur-making furnace for recycling and reuse as an acid gas source of a sulfur-making unit;
(5) After 36-48 hours of sulfur blowing, the regeneration tower is gradually changed into a cold amine circulation, and the residual acid gas is enriched in the amine liquid until the regeneration acid gas is not generated at the top of the regeneration tower;
wherein, in the step (1), the first temperature is 1100-1350 ℃;
wherein in the step (1), the amount of the air fed into the furnace is adjusted according to the amount of the natural gas fed into the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air required by each cubic meter of natural gas is controlled to be 8-9m 3 ；
In the step (1), the flow rate of the nitrogen fed with nitrogen is calculated according to the formula (1):
Q＝0.2746n 3 -9.0138n 2 +131.28n-26.718 (1)；
wherein Q is the flow rate of nitrogen (m 3 ) N is the scale of the sulfur recovery unit in tens of thousands of tons/year.
2. The sulfur recovery plant shutdown sulfur blowing method of claim 1, wherein the primary reactor inlet temperature is 220-250 ℃ and the secondary reactor inlet temperature is 210-240 ℃.
3. The sulfur recovery apparatus shutdown sulfur blowing method according to claim 1, wherein the absorption overhead temperature is controlled to be 25 to 40 ℃ and the regeneration overhead temperature is controlled to be 100 to 115 ℃.
4. The sulfur recovery apparatus shutdown sulfur blowing method according to claim 1, wherein the liquid phase outlet of the absorption column is connected to the liquid phase inlet of the regeneration column via a pipeline, and the liquid phase outlet of the regeneration column is connected to the liquid phase inlet of the absorption column via a pipeline.
5. The method for blowing sulfur out of a sulfur recovery apparatus according to claim 1, wherein in said step (1), steam is fed into a sulfur producing furnace in accordance with the amount of natural gas fed into the furnace at a rate of 1m 3 The natural gas/h is mixed with 1.9-2.3kg/h steam.
6. The method for blowing sulfur out of sulfur recovery plant shutdown according to claim 1, wherein the hydrogenation unit comprises a hydrogenation reactor and a quenching tower, and the hydrogen content in the purge tail gas of the hydrogenation unit at the outlet of the quenching tower is controlled to be more than 1vol%.
7. The method for blowing sulfur out of a sulfur recovery apparatus according to claim 1, wherein in said step (5), after 36 to 48 hours of blowing sulfur, the amount of the reboiler steam at the bottom of the regeneration tower is reduced at a rate of 3 to 4 tons per hour, the temperature of the regeneration tower is gradually reduced to 25 to 38 ℃, and the remaining acid gas is enriched in the amine liquid until no regenerated acid gas is produced at the top of the regeneration tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110425212.4A CN115215301B (en) | 2021-04-20 | 2021-04-20 | Shutdown sulfur blowing method for sulfur recovery device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110425212.4A CN115215301B (en) | 2021-04-20 | 2021-04-20 | Shutdown sulfur blowing method for sulfur recovery device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215301A CN115215301A (en) | 2022-10-21 |
| CN115215301B true CN115215301B (en) | 2024-02-13 |
Family
ID=83604033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110425212.4A Active CN115215301B (en) | 2021-04-20 | 2021-04-20 | Shutdown sulfur blowing method for sulfur recovery device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215301B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2386336A1 (en) * | 1999-10-22 | 2001-05-03 | Monsanto Company | Process for the production of sulfur |
| JP2004345904A (en) * | 2003-05-22 | 2004-12-09 | Jgc Corp | Method and apparatus for recovering sulfur |
| CN101927982A (en) * | 2010-08-27 | 2010-12-29 | 西南石油大学 | Isothermal direct oxidization recovery technology of sulfur |
| CN105480951A (en) * | 2016-01-11 | 2016-04-13 | 神华集团有限责任公司 | Liquid sulfur degassing system and liquid sulfur degassing method |
| CN106554000A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Sulphur unit green shut-down method |
| CN106829875A (en) * | 2017-03-08 | 2017-06-13 | 安徽宣城金宏化工有限公司 | A kind of handling process and equipment for carbon disulphide production Process Gas |
| CN206437872U (en) * | 2017-01-05 | 2017-08-25 | 中国石油化工股份有限公司 | Hot nitrogen blows sulphur system |
| CN108298505A (en) * | 2018-01-29 | 2018-07-20 | 华陆工程科技有限责任公司 | Processing contains H2The process integration of S sour gas while extracting sulfuric acid and sulphur |
| CN108341400A (en) * | 2018-03-12 | 2018-07-31 | 苏州富博宏新材料科技有限公司 | A kind of sulphur recovery and exhaust gas processing device shut-down process for cleanly preparing |
| CN112648628A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Ultralow-sulfur emission process for flue gas of sulfur recovery device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10752502B2 (en) * | 2018-08-02 | 2020-08-25 | Stephen L Santo | “ENRICH-SMAX”—integrated H2S removal, separation of impurities and partial acid gas enrichment in sour gas processing |
-
2021
- 2021-04-20 CN CN202110425212.4A patent/CN115215301B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2386336A1 (en) * | 1999-10-22 | 2001-05-03 | Monsanto Company | Process for the production of sulfur |
| JP2004345904A (en) * | 2003-05-22 | 2004-12-09 | Jgc Corp | Method and apparatus for recovering sulfur |
| CN101927982A (en) * | 2010-08-27 | 2010-12-29 | 西南石油大学 | Isothermal direct oxidization recovery technology of sulfur |
| CN106554000A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Sulphur unit green shut-down method |
| CN105480951A (en) * | 2016-01-11 | 2016-04-13 | 神华集团有限责任公司 | Liquid sulfur degassing system and liquid sulfur degassing method |
| CN206437872U (en) * | 2017-01-05 | 2017-08-25 | 中国石油化工股份有限公司 | Hot nitrogen blows sulphur system |
| CN106829875A (en) * | 2017-03-08 | 2017-06-13 | 安徽宣城金宏化工有限公司 | A kind of handling process and equipment for carbon disulphide production Process Gas |
| CN108298505A (en) * | 2018-01-29 | 2018-07-20 | 华陆工程科技有限责任公司 | Processing contains H2The process integration of S sour gas while extracting sulfuric acid and sulphur |
| CN108341400A (en) * | 2018-03-12 | 2018-07-31 | 苏州富博宏新材料科技有限公司 | A kind of sulphur recovery and exhaust gas processing device shut-down process for cleanly preparing |
| CN112648628A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Ultralow-sulfur emission process for flue gas of sulfur recovery device |
Non-Patent Citations (3)
| Title |
|---|
| Three-dimensional CFD simulation of industrial Claus reactors;Abdel-Fattah, AS et al.;《CHEMICAL ENGINEERING RESEARCH & DESIGN》;第112卷;第78-87页 * |
| 可控氧含量工艺在硫黄回收装置停车过程中的应用;王会强;中外能源;第25卷(第06期);第90-95页 * |
| 改良天然气吹硫工艺在硫磺回收装置的应用;郑晓薇等;《石油与天然气化工》;第49卷(第2期);第9页左栏第1、3-4段和右栏第3段、第10页左栏第1段和图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215301A (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102910593B (en) | System and method for treating waste acid gas | |
| CN100544807C (en) | The method of a kind of sulphur recovery and exhaust gas processing device and sulphur recovery thereof and vent gas treatment | |
| CA2419627C (en) | Treatment of a gas stream containing hydrogen sulphide | |
| CN102430329B (en) | Reduction of CO and NOx in regenerator flue gas | |
| US10188988B2 (en) | Claus unit treatment of shutdown tail gas | |
| CN105327599B (en) | The processing method of molten sulfur degasification exhaust gas | |
| CN103626136A (en) | Wet method used for preparing sulfuric acid from exhaust gas containing hydrogen sulfide | |
| CN204233957U (en) | A kind of novel sulfurizedization hydrogen waste gas pollution control and treatment system | |
| CN209173684U (en) | Hot nitrogen purges sulphur unit | |
| CN209652260U (en) | A kind of Crouse's sulphur recovery and exhaust treatment system | |
| CN108298505A (en) | Processing contains H2The process integration of S sour gas while extracting sulfuric acid and sulphur | |
| CN210973883U (en) | Sulfur recovery device is blown in circulation | |
| EP1899042A1 (en) | Treatment of fuel gas | |
| CN205381962U (en) | Molten sulfur degasification system | |
| CN201031142Y (en) | Sulfur recovery and exhaust gas treating device of reheat furnace hydrogen making | |
| CN115215301B (en) | Shutdown sulfur blowing method for sulfur recovery device | |
| CN202864918U (en) | Waste gas treatment system of acid gas | |
| CN106268230A (en) | A kind of waste heat of coke-oven flue gas reclaim and purify system and technique | |
| CN113264508B (en) | Sulfur recovery method and device | |
| CN115594154B (en) | Sulfur recovery device capable of realizing green shutdown and shutdown sulfur blowing method thereof | |
| CN112299379B (en) | Sulfur recovery device filled with oxidation state hydrogenation catalyst and start-up method | |
| CN220310145U (en) | Sulfur recovery device is blown to hot nitrogen | |
| CN205011386U (en) | Claus tail gas clean up system | |
| CN219572720U (en) | Sulfur recovery shutdown hot nitrogen sulfur blowing device | |
| CN217676822U (en) | Clean passivating device for sulfur recovery section after feed gas stops conveying |
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 |