CN115215301A - Shutdown sulfur blowing method of sulfur recovery device - Google Patents
Shutdown sulfur blowing method of sulfur recovery device Download PDFInfo
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- CN115215301A CN115215301A CN202110425212.4A CN202110425212A CN115215301A CN 115215301 A CN115215301 A CN 115215301A CN 202110425212 A CN202110425212 A CN 202110425212A CN 115215301 A CN115215301 A CN 115215301A
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 295
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 293
- 239000011593 sulfur Substances 0.000 title claims abstract description 291
- 238000007664 blowing Methods 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 99
- 238000011084 recovery Methods 0.000 title claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 191
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 148
- 230000008929 regeneration Effects 0.000 claims abstract description 101
- 238000011069 regeneration method Methods 0.000 claims abstract description 101
- 239000007788 liquid Substances 0.000 claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 claims abstract description 94
- 238000010521 absorption reaction Methods 0.000 claims abstract description 87
- 239000003345 natural gas Substances 0.000 claims abstract description 74
- 150000001412 amines Chemical class 0.000 claims abstract description 73
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 71
- 239000002253 acid Substances 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000010926 purge Methods 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 claims abstract description 12
- 230000001502 supplementing effect Effects 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 238000010791 quenching Methods 0.000 claims description 43
- 230000000171 quenching effect Effects 0.000 claims description 21
- 239000002918 waste heat Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 19
- 230000008569 process Effects 0.000 description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 239000003546 flue gas Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—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
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- 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
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- Treating Waste Gases (AREA)
Abstract
A shutdown sulfur blowing method for a sulfur recovery device comprises the following steps: (1) After the amount of acid gas entering the sulfur production furnace is reduced, introducing natural gas into the sulfur production furnace for blending combustion, adjusting air distribution to enable the natural gas to be combusted in a secondary equivalent manner, and supplementing steam and nitrogen into the sulfur production furnace; (2) The sulfur production unit purging tail gas enters a hydrogenation unit to generate a hydrogenation unit purging tail gas; (3) The purge tail gas of the hydrogenation unit enters an absorption regeneration unit to remove H 2 Discharging the purified tail gas after S to an incinerator for incineration and then discharging; (4) Absorption of H 2 The rich amine liquid after S enters a regeneration tower to carry out amine liquid regeneration; returning the regenerated acid gas at the top of the regeneration tower to the sulfur production furnace for recycling; (5) After blowing sulfur for 36-48 hours, the regeneration tower is gradually changed into cold amine circulation, and the residual acid gas is enriched in amine liquid until no regenerated acid gas is generated at the top of the regeneration tower. The method is not limited by a single or multiple sulfur recovery devices in a workshop, is simple to operate, and does not cause 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 a shutdown sulfur blowing process 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, the sulfur recovery device at home and abroad mainly adopts a Claus + reduction absorption process. In the process, the acid gas is first burnt in a combustion furnace at high temperature, wherein the hydrocarbons and NH are present 3 Is completely oxidatively decomposed, and H 2 S is incompletely combusted, about 60-65% of S is directly converted into elemental sulfur, and then subjected to two-stage or three-stage catalytic conversion to generate low-temperature Claus reaction, wherein H in Claus tail gas 2 S and SO 2 And the S which is not collected is subjected to hydrogenation reduction and then returns to the sulfur production unit through an amine liquid system for treatment, purified gas is discharged after being incinerated by an incinerator, and the sulfur recovery rate reaches over 99.8 percent.
In recent years, the environmental protection standard of China is increasingly strict, and the emission standard GB31570-2015 of pollutants for petroleum refining industry released in 2015 specifies that the flue gas SO of a sulfur recovery device 2 Emission concentration limit value is generally required to be less than 400mg/m in regions 3 The requirement of the key area is less than 100mg/m 3 . Because the concentration of the acid gas is lower when the sulfur recovery device is shut down, the sulfur production furnace can not keep stable flame, more Claus tail gas is adopted to directly go to the incinerator through cross-line during the shutdown period of the traditional sulfur recovery device, and the method is used for SO 2 The discharge amount is often more than 30000mg/m 3 The other method adopts gas for combustion supporting, and the air distribution of the gas is greatly influenced by factors such as composition change and the like, so that forced shutdown is easily caused due to the fact that carbon deposition or peroxide deactivates the catalyst, bed pressure drop is increased and the likeThe problem of the shutdown method of the sulfur recovery device is urgently solved.
CN103566730A discloses a method for treating sulfur-removing purge tail gas generated during shutdown of a sulfur recovery device, the method uses sulfur dioxide generated by completely burning raw material acid gas to purge a claus unit, the sulfur-removing purge tail gas is sent to a tail gas system to be treated, and the reduction of the concentration of sulfur dioxide in the discharged flue gas is realized by controlling the hydrogenation reduction condition. The method needs to inject excessive air into the sulfur production furnace when the raw material acid gas is completely combusted, and once the condition of over oxygen occurs in the sulfur blowing operation process, the temperature runaway of the system is easily caused, the amine liquid is easily degraded, the burden of an absorption regeneration system is increased, and in addition, the tail gas in the later stage of sulfur removal cannot be well treated.
CN206447572U discloses a hot nitrogen purging sulfur recovery device, a sulfur production combustion furnace, a waste heat boiler and a first-stage sulfur condenser are sequentially connected, a second-stage sulfur condenser is arranged between a first-stage reactor and a second-stage reactor, a third-stage sulfur condenser is arranged at the outlet of the second-stage reactor, liquid sulfur outlets of the first-stage, second-stage and third-stage sulfur condensers are connected with a liquid sulfur pool, a gas outlet of the third-stage sulfur condenser is connected with a tail gas treatment device, nitrogen is heated by a nitrogen heater and then is connected to the outlet of the waste heat boiler, the inlets of the first-stage reactor and the second-stage reactor, and a hot air purging pipeline is arranged at the inlet of the first-stage reactor and/or the second-stage reactor. The device consumes nitrogen and takes a lot of and need increase nitrogen gas heating facility, increases the device energy consumption, and in addition, the device need cut off raw materials acid gas when stopping, only is applicable to the shut-down of two sets and above sulphur device.
CN105819404A discloses a zero-discharge shutdown process of a sulfur recovery device, in the shutdown sulfur blowing and hydrogenation reactor catalyst passivation period, shutdown tail gas is introduced into an incinerator from the front of a quench tower to be incinerated and then absorbed SO by an alkali liquor absorption tower 2 The method belongs to a post-alkali washing process, has high construction and operation cost and serious corrosion, and simultaneously produces waste alkali liquor to form new pollution.
In order to solve the technical problem, the invention provides a shutdown sulfur blowing method of a sulfur recovery device.
Disclosure of Invention
The invention aims to provide a sulfur recovery device shutdown sulfur blowing method, which can solve the problem that the tail gas blown by a sulfur production unit during shutdown sulfur blowing directly goes to an incinerator through an overline SO as to influence the SO in flue gas 2 The problem of discharge 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 devices in the whole shutdown sulfur blowing process reach the discharge standard, and the sulfur recovery devices are widely applied to the shutdown sulfur blowing process of the sulfur recovery devices adopting the Claus + reduction absorption process in the industries of petroleum refining, natural gas purification, coal chemical industry and the like.
Therefore, the invention provides a shutdown sulfur blowing method of a sulfur recovery device, which adopts a device comprising a sulfur production unit, a hydrogenation unit, an absorption regeneration unit, an incinerator and a chimney which are sequentially connected, wherein the sulfur production unit comprises a sulfur production 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 separation tank, the hydrogenation unit comprises a tail gas heater, a hydrogenation reactor, a steam generator and a quench 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 production furnace is reduced and the reaction temperature in the sulfur production furnace of the sulfur production unit is difficult to maintain at a first temperature, introducing natural gas into the sulfur production furnace for co-combustion, adjusting air distribution to enable the natural gas to be combusted in a sub-equivalent manner, and supplementing steam and nitrogen into the sulfur production furnace, so that the reaction temperature in the sulfur production furnace is maintained at the first temperature, carbon and peroxide are prevented from being precipitated by a system, the tail gas swept by the sulfur production unit generated by the sulfur production unit can sequentially enter a hydrogenation unit and an absorption regeneration unit, and the tail gas does not need to enter an incinerator through crossing lines;
(2) The purge tail gas of the sulfur production unit enters a hydrogenation unit, wherein the purge tail gas is not H 2 Hydrogenation of S-containing compounds to H 2 S, obtaining a product containing H 2 S, blowing tail gas by a hydrogenation unit;
(3) The hydrogenation unit sweeps tail gas to enter an absorption tower of an absorption regeneration unit, wherein the hydrogenation unit sweeps H in the tail gas 2 S is absorbed by lean amine liquid in the absorption tower to remove H 2 Discharging the purified tail gas after S to an incinerator for incineration through the top of the absorption tower;
(4) Absorbing H in the absorption tower 2 The rich amine liquid after S enters a regeneration tower to carry out amine liquid regeneration; returning the regenerated acid gas at the top of the regeneration tower to the sulfur production furnace for recycling as an acid gas source of the sulfur production unit;
(5) After blowing sulfur for 36-48 hours, the regeneration tower is gradually changed into cold amine circulation, and the residual acid gas is enriched in 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, the sulfur production unit comprises: the system 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, a tail gas liquid separating tank, 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 pipeline. Wherein, the temperature of a hearth of the sulfur production 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 comprises: the tail gas heating device, the hydrogenation reactor, the steam generator, the quench tower, the pipelines for connecting the devices, the delivery pump and the valves arranged on the connecting pipelines and the instrument device for automatic control are connected in sequence. 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 conveying pump, a valve and an instrument device for automatic control, wherein the pipeline is connected with the absorption tower and the regeneration tower in sequence, the conveying pump, the valve and the instrument device are arranged on the connecting pipeline, a liquid phase outlet of the absorption tower is connected with a liquid phase inlet of the regeneration tower through a pipeline, and a liquid phase outlet of the regeneration tower is connected with a liquid phase inlet of the absorption tower through a pipeline.
The tail gas purged by the sulfur production unit refers to the purged tail gas at the outlet of the tail gas separating tank.
Wherein, the hydrogenation unit purging tail gas refers to the purging tail gas at the outlet of the top of the quenching tower.
Wherein the tail gas purification refers to the removal of H from the hydrogenation unit sweeping tail gas in an absorption tower 2 And (4) absorbing tower top outlet gas after S.
Wherein, in the step (1), the first temperature is 1100-1350 ℃.
In the step (1), the amount of the natural gas 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 8-9.5m of air is required for each cubic meter of the natural gas 3 Preferably 8.5 to 9m 3 。
In the step (1), steam is supplemented into the sulfur production furnace according to the amount of the natural gas fed into the furnace, and the steam is added according to the proportion of 1m 3 The natural gas/h is mixed with 1.9 to 2.3kg/h steam, preferably 1.9 to 2.1kg/h steam.
In the step (1), the temperature of the sulfur production furnace may be slightly high due to a large combustion heat value of natural gas, nitrogen gas needs to be supplemented into the sulfur production furnace according to the temperature of the sulfur production furnace (controlled at 1100-1350 ℃) in the sulfur blowing process, the sulfur-carrying and heat-carrying gas amount of the sulfur production system is increased, and the local over-temperature of equipment is avoided, wherein the nitrogen gas amount supplemented with nitrogen gas 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) of nitrogen gas 3 ) And n is the scale of the apparatus (ten thousand tons/year).
Wherein, in the step (2), the sulfur production unit purges S and SO in the tail gas 2 In the hydrogenation unit, under the action of catalyst in the hydrogenation reactor, it is reduced to produce H 2 S, the reaction process is shown as formulas (2) to (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 production unit purges SO in tail gas 2 And S is hydrogenated in a hydrogenation reactor to generate H 2 And the S gas is cooled by a steam generator and a quench tower and then is discharged from an outlet of the quench tower as a hydrogenation unit blowing tail gas.
Wherein, a hydrogen on-line analyzer is arranged at the gas outlet of the 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%, preferably 2-4vol%.
Wherein, the pH value of the quenching tower is controlled between 7 and 9, and alkali injection measures are taken when 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 the lean amine liquid in the absorption tower to absorb H 2 And S, discharging the purified tail gas at the top of the absorption tower to an incinerator for incineration and then discharging, wherein the temperature at the top of the absorption tower is controlled to be 25-40 ℃, and preferably 25-38 ℃.
Wherein in the step (4), H is absorbed in the absorption tower 2 And discharging the rich amine liquid after S through the bottom of the absorption tower, feeding the rich amine liquid into the upper part of a 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 production furnace through the top of the regeneration tower to be recycled as the acid gas source of the sulfur production unit, and the sulfur production unit can continuously produce sulfur, so that the sulfur resource during the sulfur blowing period is effectively utilized.
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, and the temperature at the top of the regeneration tower is controlled to be 100-115 ℃, the temperature at the bottom of the regeneration tower is controlled to be 115-120 ℃, and the pressure at the top of the regeneration tower is controlled to be 0.06-0.10Mpa.
Wherein the regenerated acid gas specifically refers to high-concentration H-containing gas separated from the rich amine solution 2 S gas, wherein the high concentration means a concentration of 50 to 95 vol%.
In the step (5), after sulfur blowing is carried out for 36-48 hours, the steam quantity of a reboiler at the bottom of the regeneration tower is reduced at a rate of reducing 3-4 tons per hour, the temperature of the regeneration tower is gradually reduced to 25-38 ℃, the residual acid gas is enriched in amine liquid until no regenerated acid gas is generated at the top of the regeneration tower, and after the enrichment is finished, the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom pump and then is introduced into an amine liquid storage tank.
The invention has the following beneficial technical effects:
(1) The method can ensure the sulfur production unit and hydrogenation during the shutdown sulfur blowing period of the sulfur recovery deviceThe normal operation of the unit and the absorption regeneration unit can solve the problem that the tail gas blown by the sulfur production unit directly goes to the incinerator through overline during the shutdown sulfur blowing period of the sulfur recovery device to cause the flue gas SO 2 The problem of excessive discharge is particularly suitable for the shutdown process of a single set of sulfur recovery device, the shutdown process is not limited by a single set or multiple sets of sulfur recovery devices in a workshop, the sulfur recovery device reaches the discharge standard in the whole shutdown process, the operation is simple, and no secondary pollution or SO is caused 2 The emission reduction is obvious.
(2) In the step (1) of the method, natural gas is introduced into the sulfur production furnace for blending combustion, air distribution is adjusted to enable the natural gas to be combusted in a sub-equivalent manner, and steam and nitrogen are supplemented into the sulfur production furnace, so that carbon and peroxide are prevented from being precipitated by a system while the reaction temperature in the sulfur production furnace is maintained at a first temperature, a hydrogenation unit and an absorption regeneration unit are protected, and the sweeping tail gas generated by the sulfur production unit can sequentially enter the hydrogenation unit and the absorption regeneration unit without going to the incinerator through crossing lines. The specific reasons are as follows:
the air distribution deviation of the blowing process of the sulfur production unit is large during the traditional shutdown sulfur blowing period of the sulfur recovery device, the influence on the hydrogenation unit catalyst and the amine liquid of the absorption regeneration unit is obvious, and a sulfur blowing system needs to be cut out of the hydrogenation unit and the absorption regeneration unit during sulfur blowing.
In the method of the invention:
(i) Through controlling the sub-equivalent burning of the natural gas, the degradation loss of the amine liquid caused by the over-oxidation of the system can be prevented, the quality of the amine liquid of the absorption and regeneration unit is ensured, and the absorption and regeneration unit normally operates during the shutdown and sulfur blowing of the sulfur recovery device.
(ii) Steam is injected into the sulfur production furnace to react with CO, C and the like generated by incomplete combustion of natural gas so as to avoid carbon precipitation of the catalyst, and meanwhile, a certain amount of H can be provided for the hydrogenation reactor 2 (the reaction process is shown in formulas (4) to (5)), 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. Thereby avoiding the blowing tail gas generated by the sulfur-making unit from entering the incinerator through crossing the line to cause the flue gas SO 2 Emission exceeds standardTo (3) is described.
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 upstream device is not required to be cut off to feed the acid gas into the furnace, the regenerated acid gas generated by the device is returned to the sulfur making furnace in the early stage to be recycled as the acid gas source of the sulfur making unit, and is enriched in the amine liquid in the later stage without being sent to the sulfur recovery device without shutdown 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 suitable for sulfur recovery devices adopting processes such as gas-gas heat exchange, high-temperature blending, electric heating, heating furnaces and the like.
(5) The shutdown sulfur blowing method can ensure that the flue gas SO is generated during the shutdown sulfur blowing period of the whole sulfur device 2 The discharge is less than 100mg/m 3 And the standard discharge in the shutdown process is realized.
Brief description of the drawings
FIG. l is a flow chart of the shutdown sulfur blowing method of the sulfur recovery device of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
FIG. 1 shows a flow chart of the shutdown sulfur blowing method of the sulfur recovery unit of the 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 production furnace; 7. a waste heat boiler; 8. a first-stage condenser; 9. a primary heater; 10. a first stage reactor; 11. a secondary condenser; 12. a secondary heater; 13. a secondary reactor; 14. a third-stage condenser; 15. separating the tail gas into liquid tanks; 16. a tail gas heater; 17. a hydrogenation reactor; 18. a steam generator; 19. a quench tower; 20. a water circulating pump; 21. a circulating water cooler; 22. an absorption tower; 23. rich inA liquid pump; 24. a lean-rich liquid heat exchanger; 25. a regeneration tower; 26. a reboiler at the bottom of the regeneration tower; 27. an amine liquid storage tank; 28. a barren liquor pump; 29. a liquid sulfur pool; 30. an incinerator; 31. a chimney; 32.H 2 S/SO 2 A ratio analyzer; 33. hydrogen on-line analyzer.
The shutdown sulfur blowing method of the sulfur recovery plant of the present invention is specifically described below with reference to fig. 1, comprising:
(i) When the sulfur production unit is stopped, after the acid gas amount generated by an upstream device in the sulfur production unit is reduced, a natural gas inlet (3) is opened, and the flow of the blended natural gas is gradually increased to maintain the temperature of the sulfur production furnace;
the amount of air entering the air inlet (1) is adjusted according to the amount of natural gas 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 the natural gas 3 Preferably 8.5 to 9m 3 ；
Opening a steam inlet (4) at the same time of opening a natural gas inlet (3), supplementing steam into the sulfur production furnace according to the amount of the natural gas entering the furnace, and keeping the steam at a rate of 1m 3 1.9 to 2.3kg/h steam, preferably 1.9 to 2.1kg/h steam, per h natural gas;
opening a nitrogen inlet (5) simultaneously in the sulfur blowing process, adjusting the flow of nitrogen entering the furnace according to the formula (1), and controlling the temperature of the sulfur production furnace (6) to be 1100-1350 ℃;
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 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 enters a liquid sulfur pool (29) after being condensed by a first-stage condenser, a second-stage condenser and a third-stage condenser, and the tail gas blown by the sulfur production unit is discharged from an outlet of a tail gas liquid separation tank (15);
(ii) In the hydrogenation unit, the sweeping tail gas of the sulfur production unit sequentially enters a tail gas heater (16), a hydrogenation reactor (17), a steam generator (18) and a quench tower (19);
controlling the inlet temperature of the hydrogenation reactor to be 250-300 ℃, and controlling the content of hydrogen at the outlet of the quenching tower to be more than 1vol%, preferably 2-4vol%; observing the change of the pH value 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 sweep tail gas of sulfur production unit 2 Reduction 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 contacts with the lean amine liquid in the absorption tower (22) in a countercurrent way to absorb H 2 S, the purified tail gas at the top of the absorption tower enters a tail gas incinerator (30) for incineration and then is discharged; wherein, the temperature of the top of the absorption tower is controlled to be 25-40 ℃, preferably 25-38 ℃;
(iv) Rich amine liquid at the bottom of the absorption tower (22) enters the upper part of a regeneration tower for regeneration, lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and regenerated acid gas at the top of the regeneration tower returns to a sulfur production furnace for recycling as an acid gas source of a sulfur production unit;
wherein the temperature at the top of the regeneration tower is controlled to be 100-115 ℃, the temperature at the bottom of the regeneration tower is controlled to be 115-120 ℃, and the pressure at the top of the regeneration tower is controlled to be 0.06-0.10Mpa;
(v) After blowing sulfur for 36-48 hours, reducing the steam quantity of a reboiler (26) at the bottom of the regeneration tower at a speed of reducing 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, and after the enrichment is finished, pumping the amine liquid in the absorption tower into the regeneration tower through a tower bottom rich liquid pump (23) and introducing the amine liquid into an amine liquid storage tank (27).
Example 1
The sulfur blowing method is as follows: after the acid gas amount generated by the upstream device is reduced, the natural gas inlet (3) is opened, the flow of the co-fired natural gas is gradually increased to maintain the furnace temperature, the air amount of the air inlet (1) 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 equivalent weight for the time, wherein the air needs 9m per cubic meter of the natural gas 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur production furnace according to the amount of natural gas entering the furnace, and keeping the steam in a range of 1m 3 Mixing natural gas with 1.9kg/h steam, opening a nitrogen inlet (5) in the sulfur blowing process, and adjusting the mixture to enter the furnaceNitrogen flow 650m 3 H, controlling the temperature of the sulfur production furnace (6) to 1200 ℃. 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 first-stage condenser (8), a first-stage heater (9), a first-stage reactor (10), a second-stage condenser (11), a second-stage heater (12), a second-stage reactor (13), a third-stage condenser (14) and a tail gas liquid separating tank (15), the inlet temperature of the first-stage reactor is 233 ℃, the inlet temperature of the second-stage reactor is 213 ℃, sulfur generated in the sulfur blowing process enters a liquid sulfur pool (29) after being condensed by the first-stage, second-stage and third-stage condensers, the sulfur making unit blowing 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 quench tower (19), the inlet temperature of the hydrogenation reactor is 256 ℃, the hydrogen content at the outlet of the quench tower is controlled at 3vol%, and S and SO in the sulfur making unit blowing tail gas 2 Reduction under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quench tower (19), introducing the purge tail gas after hydrogenation reduction into the lower part of an absorption tower (22), and absorbing H by countercurrent contact with lean amine liquid in the absorption tower (22) 2 S, the purified tail gas at the top of the tower enters a tail gas incinerator (30) to be incinerated and then discharged, the rich amine liquid at the bottom of an absorption tower (22) enters the upper part of a regeneration tower to be regenerated, the poor 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 tower returns to a sulfur production furnace to be recycled as an acid gas source of a sulfur production unit. Observing the change of the pH value of the quenching tower at any time in the sulfur blowing process, controlling the pH value of the quenching tower at 8, and taking alkali injection measures if necessary, wherein the absorption tower top temperature is 30 ℃, the regeneration tower top temperature is 107 ℃, the tower kettle temperature is 118 ℃, and the tower top pressure is 0.08Mpa. After blowing sulfur for 37 hours, reducing the steam amount of a reboiler (26) at the bottom of the regeneration tower at a rate of reducing 3 tons per hour, gradually reducing the temperature of the regeneration tower to 30 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the tower, and introducing the amine liquid in the absorption tower into the regeneration tower through a tower bottom rich liquid pump (23) and then introducing the amine liquid into an amine liquid storage tank (27) after the enrichment is finished.
Compared with the traditional shutdown method, the method in the embodiment 1 solves the problem that the excessive emission is caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like, and the flue gas SO in the shutdown sulfur blowing period is adopted 2 The discharge is less than 80mg/m 3 And meets the latest environmental protection requirement.
Comparative example 1
When a certain 10 ten thousand tons/year sulfur recovery device is shut down, the traditional shut down sulfur blowing method is adopted, namely the Claus tail gas is burnt in the incinerator through a cross line to form the flue gas SO 2 The discharge is 20000mg/m 3 Left and right.
Example 2
The shutdown of a certain 8 ten thousand ton/year sulfur device is carried out by the following sulfur blowing method: after the acid gas amount generated by the upstream device is reduced, the natural gas inlet (3) is opened, the flow of the co-combustion natural gas is gradually increased to maintain the furnace temperature, the air amount of the air inlet (1) is adjusted according to the amount of the natural gas entering the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air requirement of each cubic meter of the natural gas is 8.5m 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur production furnace according to the amount of natural gas entering the furnace, and keeping the steam in a range of 1m 3 The natural gas/h is mixed with 2.05kg/h steam, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow rate of nitrogen entering the furnace is adjusted to be 590m 3 H, controlling the temperature of the sulfur production furnace (6) to 1190 ℃. 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 first-stage condenser (8), a first-stage heater (9), a first-stage reactor (10), a second-stage condenser (11), a second-stage heater (12), a second-stage reactor (13), a third-stage condenser (14) and a tail gas separating tank (15), the inlet temperature of the first-stage reactor is 240 ℃, the inlet temperature of the second-stage reactor is 220 ℃, sulfur generated in the sulfur blowing process enters a liquid sulfur pool (29) after being condensed by the first-stage, second-stage and third-stage condensers, the sulfur making unit blowing tail gas at the outlet of the tail gas separating tank (15) sequentially enters the tail gas heater (16), a hydrogenation reactor (17), a steam generator (18) and a quench tower (19), the inlet temperature of the hydrogenation reactor is 260 ℃, the hydrogen content at the outlet of the quench tower is controlled at 4vol%, and S and SO in the sulfur making unit blowing tail gas 2 Reduction under the action of hydrogenation catalyst to generate H 2 S, cooling the hydrogen-containing gas by a steam generator (18) and a quench tower (19), feeding the hydrogenation-reduced sweeping tail gas into the lower part of an absorption tower (22), and carrying out 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 enters a tail gas incinerator (30) to be incinerated and then discharged, the rich amine liquid at the bottom of an absorption tower (22) enters the upper part of a regeneration tower to be regenerated, the poor amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and the lean amine liquid at the top of the tower returns to the upper part of the absorption towerThe regenerated acid gas is returned to the sulfur production furnace for recycling as an acid gas source of the sulfur production unit. Observing the change of the pH value of the quenching tower at any time in the sulfur blowing process, controlling the pH value of the quenching tower at 9, and adopting alkali injection measures if necessary, wherein the absorption tower top temperature is 28 ℃, the regeneration tower top temperature is 105 ℃, the tower kettle temperature is 117 ℃, and the tower top pressure is 0.082Mpa. After sulfur blowing is carried out for 40 hours, the steam quantity of a reboiler (26) at the bottom of the regeneration tower is reduced at the rate of reducing 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 tower top, and after the enrichment is finished, the amine liquid in the absorption tower is pumped into the regeneration tower through a tower bottom enriched liquid pump (23) and then is introduced into an amine liquid storage tank (27).
Compared with the traditional shutdown method, the method in the embodiment 2 solves the problem that the excessive emission is caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like, and the flue gas SO in the shutdown sulfur blowing period is adopted 2 The discharge is less than 60mg/m 3 And meets the latest environmental protection requirement.
Comparative example 2
When a certain 8-million ton/year sulfur recovery device is shut down, the traditional shut-down sulfur blowing method is adopted, namely, the Claus tail gas is burnt in an incinerator through a cross line to obtain the SO of the flue gas 2 The emission was 24000mg/m 3 Left and right.
Example 3
The shutdown of a certain 12 ten thousand tons/year sulfur device is carried out by the following sulfur blowing method: after the acid gas amount generated by the upstream device is reduced, the natural gas inlet (3) is opened, the flow of the co-combustion natural gas is gradually increased to maintain the furnace temperature, the air amount of the air inlet (1) is adjusted according to the amount of the natural gas entering the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air requirement of each cubic meter of the natural gas is 8.8m 3 Opening a natural gas inlet (3) and a steam inlet (4), supplementing steam into the sulfur production furnace according to the amount of the natural gas entering the furnace, and controlling the steam to be in a range of 1m 3 The natural gas is mixed with 2kg/h steam, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow rate of nitrogen entering the furnace is adjusted to be 720m 3 H, controlling the temperature of the sulfur production furnace (6) to be 1220 ℃. Sulfur blowing process gas generated by a sulfur making furnace (6) in a sulfur making unit sequentially enters a waste heat boiler (7), a first-stage condenser (8), a first-stage heater (9), a first-stage reactor (10), a second-stage condenser (11), a second-stage heater (12), a second-stage reactor (13) and a third-stage condenser(14) The tail gas liquid separation tank (15), the inlet temperature of the primary reactor is 236 ℃, the inlet temperature of the secondary reactor is 215 ℃, sulfur generated in the sulfur blowing process enters the liquid sulfur pool (29) after being condensed by the primary, secondary and tertiary condensers, a sulfur production unit at the outlet of the tail gas liquid separation tank (15) sweeps tail gas and sequentially enters the tail gas heater (16), the hydrogenation reactor (17), the steam generator (18) and the quench tower (19), the inlet temperature of the hydrogenation reactor is 251 ℃, the hydrogen content at the outlet of the quench tower is controlled to be 2.5vol%, and the sulfur production unit sweeps S and SO in the tail gas 2 Reduction under the action of hydrogenation catalyst to generate H 2 S, cooling by a steam generator (18) and a quench tower (19), introducing the purge tail gas after hydrogenation reduction into the lower part of an absorption tower (22), and absorbing H by countercurrent contact with lean amine liquid in the absorption tower (22) 2 S, the purified tail gas at the top of the tower enters a tail gas incinerator (30) to be incinerated and then discharged, the rich amine liquid at the bottom of an absorption tower (22) enters the upper part of a regeneration tower to be regenerated, the poor 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 tower returns to a sulfur production furnace to be recycled as an acid gas source of a sulfur production unit. The pH value change of the quenching tower is observed at any moment in the sulfur blowing process, the pH value of the quenching tower is controlled to be 7, and alkali injection measures are adopted if necessary, the absorption tower top temperature is 29 ℃, the regeneration tower top temperature is 109 ℃, the tower kettle temperature is 119 ℃, and the tower top pressure is 0.079Mpa. After blowing sulfur for 39 hours, reducing the steam quantity of a reboiler (26) at the bottom of the regeneration tower at a speed of reducing 3.2 tons per hour, gradually reducing the temperature of the regeneration tower to 29 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the tower, and after the 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 introducing the amine liquid into an amine liquid storage tank (27).
Compared with the traditional shutdown method, the method solves the problem that the standard exceeding discharge is caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like, and the flue gas SO is generated during shutdown sulfur blowing by adopting the method 2 The discharge is less than 70mg/m 3 And meets the latest environmental protection requirement.
Comparative example 3
When a certain 12 ten thousand tons/year sulfur recovery device is shut down, the traditional shut down sulfur blowing method is adopted, namely the Claus tail gas is burnt in the incinerator through a cross line to form the flue gas SO 2 The discharge was 25000mg/m 3 Left and right.
Example 4
The shutdown of a certain 15 ten thousand tons/year sulfur device is carried out by the following sulfur blowing method: after the acid gas amount generated by the upstream device is reduced, the natural gas inlet (3) is opened, the flow of the co-fired natural gas is gradually increased to maintain the furnace temperature, the air amount of the air inlet (1) 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 equivalent weight for the time, wherein the air required by each cubic meter of the natural gas is 8.6m 3 Opening a natural gas inlet (3) and a steam inlet (4) at the same time, supplementing steam into the sulfur production furnace according to the amount of natural gas entering the furnace, and keeping the steam in a range of 1m 3 Mixing natural gas/h with 2.1kg/h steam, opening nitrogen inlet (5) in sulfur blowing process, and adjusting furnace nitrogen flow rate to 860m 3 H, controlling the temperature of the sulfur production furnace (6) to be 1235 ℃. 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 first-stage condenser (8), a first-stage heater (9), a first-stage reactor (10), a second-stage condenser (11), a second-stage heater (12), a second-stage reactor (13), a third-stage condenser (14) and a tail gas separating tank (15), the inlet temperature of the first-stage reactor is 242 ℃, the inlet temperature of the second-stage reactor is 230 ℃, sulfur generated in the sulfur blowing process enters a liquid sulfur pool (29) after being condensed by the first-stage, second-stage and third-stage condensers, the sulfur making unit blowing tail gas at the outlet of the tail gas separating tank (15) sequentially enters the tail gas heater (16), a hydrogenation reactor (17), a steam generator (18) and a quench tower (19), the inlet temperature of the hydrogenation reactor is 255 ℃, the hydrogen content at the outlet of the quench tower is controlled at 4vol%, and S and SO in the sulfur making unit blowing tail gas 2 Reduction to H under the action of hydrogenation catalyst 2 S, cooling by a steam generator (18) and a quench tower (19), introducing the purge tail gas after hydrogenation reduction into the lower part of an absorption tower (22), and absorbing H by countercurrent contact with lean amine liquid in the absorption tower (22) 2 S, the purified tail gas at the top of the tower enters a tail gas incinerator (30) to be incinerated and then discharged, rich amine liquid at the bottom of an absorption tower (22) enters the upper part of a regeneration tower to be regenerated, lean amine liquid at the bottom of the regeneration tower returns to the upper part of the absorption tower, and regenerated acid gas at the top of the tower returns to a sulfur production furnace to be recycled as an acid gas source of a sulfur production unit. Observing the change of the pH value of the quenching tower at any time in the sulfur blowing process, controlling the pH value of the quenching tower at 8, and taking alkali injection measures if necessary, wherein the absorption tower top temperature is 28 ℃, the regeneration tower top temperature is 103 ℃, the tower kettle temperature is 117 ℃, and the tower top pressure is 0.07Mpa. After blowing the sulfur for 36 hours,reducing the steam amount of a reboiler (26) at the bottom of the regeneration tower at a speed of reducing 3.9 tons per hour, gradually reducing the temperature of the regeneration tower to 28 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the 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).
Compared with the traditional shutdown method, the method solves the problem that the standard exceeding emission is caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like, and the flue gas SO is generated during the shutdown sulfur blowing period by adopting the method 2 The discharge is less than 55mg/m 3 And meets the latest environmental protection requirement.
Comparative example 4
When a certain 15 ten thousand tons/year sulfur recovery device is shut down, the traditional shut down sulfur blowing method is adopted, namely the Claus tail gas is burnt in the incinerator through a cross line to form the flue gas SO 2 The emission is 27000mg/m 3 Left and right.
Example 5
The shutdown of a certain 5 ten thousand tons/year sulfur device is carried out by the following sulfur blowing method: after the acid gas amount generated by the upstream device is reduced, the natural gas inlet (3) is opened, the flow of the co-combustion natural gas is gradually increased to maintain the furnace temperature, the air amount of the air inlet (1) is adjusted according to the amount of the natural gas entering the furnace, so that the natural gas and the air are combusted according to the equivalent weight, wherein the air requirement of each cubic meter of the 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 production furnace according to the amount of natural gas entering the furnace, and keeping the steam in a range of 1m 3 The natural gas/h is mixed with 1.95kg/h steam, a nitrogen inlet (5) is opened in the sulfur blowing process, and the flow rate of nitrogen entering the furnace is adjusted to 430m 3 H, controlling the temperature of the sulfur production furnace (6) to be 1300 ℃. Sulfur blowing process gas generated by a sulfur making furnace (6) in a sulfur making unit sequentially enters a waste heat boiler (7), a first-stage condenser (8), a first-stage heater (9), a first-stage reactor (10), a second-stage condenser (11), a second-stage heater (12), a second-stage reactor (13), a third-stage condenser (14) and a tail gas separating tank (15), wherein the inlet temperature of the first-stage reactor is 236 ℃, the inlet temperature of the second-stage reactor is 219 ℃, sulfur generated in the sulfur blowing process enters a liquid sulfur pool (29) after being condensed by the first-stage, second-stage and third-stage condensers, and the tail gas blown by the sulfur making unit at the outlet of the tail gas separating tank (15) sequentially enters the tail gas heater (16), a hydrogenation reactor (17),A steam generator (18) and a quench tower (19), wherein the inlet temperature of the hydrogenation reactor is 259 ℃, the outlet hydrogen content of the quench tower is controlled at 4vol%, and S and SO in the sweep tail gas of the sulfur production unit 2 Reduction to H under the action of hydrogenation catalyst 2 S, cooling by a steam generator (18) and a quench tower (19), introducing the purge tail gas after hydrogenation reduction into the lower part of an absorption tower (22), and absorbing H by countercurrent contact with lean amine liquid in the absorption tower (22) 2 S, the purified tail gas at the top of the tower enters a tail gas incinerator (30) to be incinerated and then discharged, the rich amine liquid at the bottom of an absorption tower (22) enters the upper part of a regeneration tower to be regenerated, the poor 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 tower returns to a sulfur production furnace to be recycled as an acid gas source of a sulfur production unit. Observing the change of the pH value of the quenching tower at any time in the sulfur blowing process, controlling the pH value of the quenching tower at 9, and adopting alkali injection measures if necessary, wherein the absorption tower top temperature is 26 ℃, the regeneration tower top temperature is 108 ℃, the tower bottom temperature is 119 ℃, and the tower top pressure is 0.081MPa. And after sulfur blowing is carried out for 41 hours, reducing the steam quantity of a reboiler (26) at the bottom of the regeneration tower at a speed of reducing 3.5 tons per hour, gradually reducing the temperature of the regeneration tower to 26 ℃, enriching the residual acid gas in the amine liquid until no regenerated acid gas is generated at the top of the tower, and after the enrichment is finished, pumping the amine liquid in the absorption tower into the regeneration tower through a tower bottom rich liquid pump (23) and introducing the amine liquid into an amine liquid storage tank (27).
Compared with the traditional shutdown method, the method solves the problem that the standard exceeding discharge is caused by directly removing the Claus tail gas to the incinerator in the shutdown sulfur blowing stage, and the like, and the flue gas SO is generated during shutdown sulfur blowing by adopting the method 2 The discharge is less than 50mg/m 3 And meets the latest environmental protection requirement.
Comparative example 5
When a certain 5 ten thousand tons/year sulfur recovery device stops working, the traditional method of stopping working and blowing sulfur is adopted, namely the Claus tail gas is burnt in the incinerator through a cross line to form the flue gas SO 2 The discharge was 15000mg/m 3 Left and right.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (10)
1. A sulfur recovery device shutdown sulfur blowing method adopts a device comprising a sulfur production unit, a hydrogenation unit, an absorption regeneration unit, an incinerator and a chimney which are sequentially connected, wherein the sulfur production unit comprises a sulfur production 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 separation tank;
wherein the method comprises the following steps:
(1) After the acid gas amount entering the sulfur production furnace is reduced and the reaction temperature in the sulfur production furnace of the sulfur production unit is difficult to maintain at a first temperature, introducing natural gas into the sulfur production furnace for blending combustion, adjusting air distribution to enable the natural gas to be combusted in a sub-equivalent manner, and supplementing steam and nitrogen into the sulfur production furnace, so that the reaction temperature in the sulfur production furnace is maintained at the first temperature, and simultaneously, carbon and peroxide are prevented from being analyzed by a system, so that the sulfur production unit purging tail gas generated by the sulfur production unit can enter a hydrogenation unit and an absorption regeneration unit in sequence, and does not need to enter the incinerator through crossing lines;
(2) The purge tail gas of the sulfur production unit enters a hydrogenation unit, wherein the purge tail gas is not H 2 Hydrogenation of S-containing compounds to H 2 S, obtaining a product containing H 2 S hydrogenation unit sweeps tail gas;
(3) The hydrogenation unit sweeps tail gas to enter an absorption tower of an absorption regeneration unit, wherein the hydrogenation unit sweeps H in the tail gas 2 S is absorbed by lean amine liquid in the absorption tower to remove H 2 Discharging the purified tail gas after S to an incinerator for incineration through the top of the absorption tower;
(4) Absorbing H in the absorption tower 2 The rich amine liquid after S enters a regeneration tower to carry out amine liquid regeneration; the regenerated acid gas at the top of the regeneration tower returns to the sulfur production furnace for recycling as an acid gas source of the sulfur production unit;
(5) After blowing sulfur for 36-48 hours, the regeneration tower is gradually changed into cold amine circulation, and the residual acid gas is enriched in amine liquid until no regenerated acid gas is generated at the top of the regeneration tower.
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 blowing method of claim 1, wherein the temperature at the top of the absorption tower is controlled to be 25-40 ℃ and the temperature at the top of the regeneration tower is controlled to be 100-115 ℃.
4. The sulfur recovery plant shutdown sulfur blowing method of claim 1, wherein the liquid phase outlet of the absorption tower is connected to the liquid phase inlet of the regeneration tower through a pipeline, and the liquid phase outlet of the regeneration tower is connected to the liquid phase inlet of the absorption tower through a pipeline.
5. A sulfur recovery plant shutdown sulfur blowing method according to claim 1, wherein in step (1), the first temperature is 1100-1350 ℃.
6. The sulfur blowing method for shutting down the sulfur recovery plant according to claim 1, wherein in the step (1), the amount of the natural gas 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 requirement of the natural gas per cubic meter is controlled to be 8-9.5m 3 。
7. The sulfur blowing method according to claim 1, wherein in the step (1), steam is supplemented to the sulfur production furnace at a rate of 1m in accordance with the amount of natural gas fed to the furnace 3 The natural gas/h is mixed with 1.9-2.3kg/h steam.
8. The sulfur recovery plant shutdown sulfur blowing method according to claim 1, wherein in the step (1), the nitrogen flow rate of the nitrogen gas supplied is calculated by the following formula (1):
Q＝0.2746n 3 -9.0138n 2 +131.28n-26.718 (1)
wherein Q is the nitrogen flow (m) 3 ) And n is the scale of the sulfur recovery device in units of ten thousand tons/year.
9. The sulfur recovery unit shutdown sulfur blowing method of claim 1, wherein the hydrogenation unit comprises a hydrogenation reactor and a quenching tower, and the hydrogen content in the hydrogenation unit purge tail gas at the outlet of the quenching tower is controlled to be more than 1vol%.
10. The sulfur blowing method for sulfur recovery plant shutdown according to claim 1, wherein in the step (5), after blowing sulfur for 36-48 hours, the steam amount of the reboiler at the bottom of the regeneration tower is reduced at a rate of 3-4 tons per hour, the temperature of the regeneration tower is gradually reduced to 25-38 ℃, 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.
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