CN113860266A - Startup method of sulfur recovery process - Google Patents
Startup method of sulfur recovery process Download PDFInfo
- Publication number
- CN113860266A CN113860266A CN202010624168.5A CN202010624168A CN113860266A CN 113860266 A CN113860266 A CN 113860266A CN 202010624168 A CN202010624168 A CN 202010624168A CN 113860266 A CN113860266 A CN 113860266A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- acid gas
- gas
- claus
- sulfur recovery
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—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
- C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- C01B17/0426—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 catalytic conversion
- C01B17/0434—Catalyst compositions
-
- 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
- C01B17/0452—Process control; Start-up or cooling-down procedures of the Claus process
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/50—Control or safety arrangements
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Abstract
The invention belongs to the technical field of sulfur recovery, and particularly relates to a startup method of a sulfur recovery process. The start-up method of the sulfur recovery process of the invention introduces acid gas into the absorption tower for enrichment absorption and regeneration during start-up, and introduces liquid sulfur into the sulfur production furnace for reaction; the acid gas to be regenerated can be arranged at the rear part of the sulfur carrying furnace, the rear part of the waste heat boiler and the primary heaterSO generated by any position in front of the front and first-stage reactors and reaction2Mixing for subsequent reaction; when the acid gas is stable and the system load meets the requirement, the introduction of the liquid sulfur is stopped, and the acid gas is directly introduced into the sulfur production furnace for direct reaction, so that the device can normally produce. The method can solve the problem that the low-concentration acid gas at the initial startup stage cannot be treated and directly burned by a torch or introduced into a sulfur production furnace of a sulfur recovery device to cause high organic sulfur content SO as to influence the SO content of the flue gas2The problem of discharge ensures that the sulfur recovery device reaches the standard and discharges in the whole start-up process.
Description
Technical Field
The invention belongs to the technical field of sulfur recovery, and particularly relates to a sulfur recovery process starting process suitable for petroleum refining, coal chemical industry and natural gas purification industry, in particular to a sulfur recovery starting method with low acid gas concentration at the initial starting stage.
Background
Sulfides in crude oil or coal can be converted into highly toxic substances H in the processing process2S, has great toxic and harmful effects on human bodies and the environment, needs to be subjected to harmless treatment, and is a sulfur recovery process correspondingly adopted as the most appropriate process. The sulfur recovery refers to a chemical process for converting sulfides in toxic sulfur-containing gases such as hydrogen sulfide and the like into elemental sulfur, thereby changing waste into valuable and protecting the environment. In a chemical plant taking coal as a raw material, the flow of processing and recycling acid gas is mainly coal → coal chemical industry → desulfurization → H2S → sulfur recycling → sulfur.
At present, the sulfur recovery technology mainly comprises a Claus + SCOT process, a super/super Yokous process and a Lo-Cat processAnd the like. Wherein, the Claus + SCOT process is widely applied due to the characteristics of high sulfur recovery rate, wide application range and the like. The Claus + SCOT process is that acid gas is combusted in a combustion furnace, wherein NH is contained3And the hydrocarbon component is completely oxidatively decomposed, and H2S is not completely combusted, about 60-65% of S is directly converted into elemental sulfur, and the rest is H2S is converted into SO by 1/32，H2S and SO2Low-temp Claus reaction under the condition of catalyst to obtain sulfur with conversion rate up to 97% or more and residual H2S and SO2And the S which is not trapped is subjected to hydrogenation reduction and absorption regeneration, so that the sulfur yield of the device reaches more than 99.9 percent. According to the difference of the concentration of the treated acid gas, the Claus process is divided into a direct current method and a flow dividing method, the direct current method is generally adopted for treating the acid gas with the concentration of 50-100%, the direct current method for preheating the acid gas and air is generally adopted for treating the acid gas with the concentration of 30-50%, the flow dividing method is generally adopted for treating the acid gas with the concentration of 15-30%, the flow dividing method for preheating the acid gas and air is generally adopted for treating the acid gas with the concentration of 5-15%, and fuel gas is properly mixed.
According to the regulation of the emission standard GB31570-2015 for the industrial pollutants for refining petroleum, the limit value of the emission concentration of the atmospheric pollutants of the sulfur recovery device is less than 400mg/Nm3Standard, special local execution less than 100mg/Nm3. But the regulation does not apply to the flue gas SO during the start-up and shut-down periods of the sulfur recovery plant2The emission concentration is regulated, so if the requirements of the emission standard GB31570-2015 of the petroleum refining industry pollutants are met during the startup and shutdown period, the sulfur recovery device is greatly tested during the startup and shutdown period. In the initial start-up period, the concentration of the acid gas is low, so that when the sulfur device is introduced, the load of the device is low, and the sulfur making furnace cannot keep stable flame. Therefore, the existing method adopts a large amount of discharged torches to burn off, but causes great environmental pollution. At present, another feasible method is to adopt gas or natural gas for combustion supporting, air distribution is greatly influenced by factors such as flow meters, composition changes and the like, but forced shutdown such as catalyst inactivation, bed pressure drop increase and the like caused by carbon deposition is very easy to cause; meanwhile, because natural gas and gas are introduced, the gas can be generated in the sulfur production furnaceLarge amount of CO2And CO2The existence of the sulfur can cause a plurality of side reactions, and a plurality of organic sulfur is generated in the sulfur production furnace, thereby bringing burden to the subsequent catalyst and influencing the flue gas SO of the device2And (5) discharging.
For example, chinese patent CN105819404A discloses a zero discharge shutdown process of a sulfur recovery device, the startup method of which comprises: firstly, during the startup of a furnace, the flue gas of the furnace directly enters an alkali liquor absorption tower; secondly, during the temperature rise of the converter, tail gas from the tail gas separating tank enters an incinerator for incineration, and the obtained high-temperature flue gas is recycled by a tail gas waste heat boiler to enter an alkali liquor absorption tower; during the presulfurization of hydrogenation reactor catalyst, hydrogen sulfide in the process gas of sulfur production is used to presulfurize hydrogenation reactor catalyst, its concentration is controlled by ratio analyzer, and the hydrogenation tail gas is introduced into incinerator from the front of quench tower and incinerated, and then absorbed SO by alkali liquor absorption tower2. However, the method belongs to a post-alkali washing process, not only has high construction and operation cost and serious corrosion, but also can generate waste alkali liquor simultaneously to form new pollution.
For another example, chinese patent CN202829575U discloses a sulfur recovery device, which introduces raw acid gas into a hydrogenation reactor to pre-sulfurize a hydrogenation catalyst while raising the temperature of the furnace at the start-up point of the whole sulfur recovery device, thereby realizing the synchronous start-up of a claus unit and a tail gas purification unit. However, the device still cannot treat low-concentration acid gas at the initial startup, exhaust emission exceeds the standard easily caused by introducing tail gas hydrogenation unit process gas into the ignition furnace and the Claus unit process gas, catalyst temperature runaway is easily caused during the startup, the emission reaching the standard in the whole startup process cannot be met, and the defect that the low-concentration acid gas cannot be treated particularly at the initial startup is still existed.
Therefore, it is urgent to develop a sulfur recovery process that can sufficiently solve the above problems, especially, the treatment of low concentration acid gas at the initial stage of start-up.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a startup method of a sulfur recovery process, which can solve the problem that low-concentration acid gas at the initial startup stage cannot be treated and directly burned by a torch or introduced into a sulfur recovery deviceThe sulfur production furnace causes high organic sulfur content to influence the SO of flue gas2The problem of emission to ensure that the sulfur recovery device reaches the standard and emits in the whole start-up process, the operation is simple, and secondary pollution and SO are not caused2The emission reduction is obvious, and the method is widely applied to sulfur recovery devices and start-up processes in industries such as petroleum refining, natural gas purification and coal chemical industry.
In order to solve the technical problem, the start-up method of the sulfur recovery process comprises the following steps:
(1) in the initial stage of start-up, directly introducing the acidic gas generated by the upstream device into the absorption tower for enrichment absorption, and detecting H in the absorption tower2When the concentration of S reaches a preset value, starting a regeneration tower to perform amine liquid cyclic regeneration treatment, and collecting the regenerated acid gas for later use;
(2) inputting the liquid sulfur to be treated into a sulfur production furnace, and completely combusting the liquid sulfur according to air distribution to generate SO2；
(3) SO after combustion2Mixing with the regenerated acid gas, performing Claus reaction, and condensing and recovering the obtained liquid sulfur; the produced Claus tail gas is subjected to hydrogenation reaction treatment to carry out tail gas treatment.
Specifically, in the step (1), the acidic gas is introduced into the absorption tower directly without heating after liquid separation.
Specifically, the step (1) further comprises the step of starting an incinerator to treat the tail gas generated by acid gas regeneration, wherein the temperature rise rate of the incinerator is controlled to be 10-25 ℃/h, and the incinerator is preferably ignited by natural gas. In the whole process, the acid gas is introduced into the absorption tower and the ignition incinerator in no sequence.
Specifically, in the step (1), H in the amine liquid of the absorption tower is controlled2And when the S reaches 5-8g/L, starting the regeneration tower.
Specifically, in the step (1), the temperature of the absorption tower is controlled to be 20-40 ℃, and preferably 25-35 ℃; the tower top temperature of the regeneration tower is controlled to be 110-115 ℃, and the tower bottom temperature is controlled to be 115-120 ℃.
Specifically, in the step (2), when the acid gas is stable and the system load meets the requirement, the gas amount introduced into the absorption tower by the acid gas is gradually reduced, and the acid gas generated by an upstream device is slowly introduced into the sulfur production furnace until the start-up of the sulfur recovery device is completed, and the sulfur recovery device is shifted to normal production.
Specifically, in the step (2), inert gas is used as power to carry the liquid sulfur into the sulfur production furnace, and the temperature of the inert gas is controlled to be 120-140 ℃. The inert gas can be nitrogen, or can be purified gas at the top of an absorption tower or flue gas after an incinerator. The acid gas is slowly introduced to the sulfur production furnace, and particularly, the acid gas can be preheated or not; the acid gas can be fed into sulfur-making furnace by adopting direct-current process or by adopting flow-splitting process.
Specifically, in the step (2), the air distribution according to the complete combustion of the liquid sulfur, specifically, the air distribution (air) entering the sulfur production furnace, may or may not be preheated.
Specifically, in the step (3), the SO after combustion2And the regenerated acid gas is mixed at any position between the rear part of the sulfur production furnace and the inlet of the Claus reactor. The method specifically means that the rear part of a sulfur production furnace, the rear part of a waste heat boiler, the inlet of a primary heater and the inlet of a primary reactor are mixed at any position, and can be used for mixing in a single way or multiple ways, and the mixed materials sequentially enter a sulfur production unit and a tail gas treatment unit.
Preferably, the temperature of the hearth of the sulfur production furnace is controlled to be between 900 ℃ and 1400 ℃, and preferably between 1000 ℃ and 1300 ℃.
Specifically, in the step (3);
the catalyst of the claus reaction treatment step comprises a claus catalyst; the Claus reactor can be filled with Claus catalysts known in the industry, such as alumina-based sulfur production catalyst, titania-based sulfur production catalyst, oxygen removal catalyst and the like, and can be graded at will or filled completely. Preferably, in the first-stage reactor, 1/3 volumes of the oxygen-removing catalyst are filled in the upper part of the first-stage reactor, and 2/3 volumes of the titanium oxide-based sulfur-making catalyst are filled in the lower part of the first-stage reactor.
The temperature of the claus reaction step is between 200 ℃ and 250 ℃.
Specifically, in the step (3):
the catalyst in the hydrogenation reaction treatment step comprises a pre-vulcanized Claus tail gas hydrogenation catalyst, an oxidation state Claus tail gas hydrogenation catalyst or a vulcanized oxidation state Claus tail gas hydrogenation catalyst;
the temperature of the hydrogenation step is 200-250 ℃.
Specifically, in the step (3), the tail gas treatment step includes a step of introducing the tail gas into the absorption tower and a step of introducing the tail gas into the regeneration tower for regeneration.
Specifically, in the step (3), after the normal production is carried out, the space velocity of the hydrogenation reactor is controlled to be 200h in the hydrotreating step-1-1000h-1Preferably, the space velocity is controlled at 500h-1-600h-1。
The start-up method is not only limited to a sulfur recovery device adopting medium-pressure steam heat exchange, but also applicable to sulfur recovery devices adopting processes such as gas-gas heat exchange, high-temperature blending, electric heating, heating furnaces and the like.
The start-up method of the sulfur recovery process of the invention introduces acid gas into the absorption tower for enrichment absorption and regeneration during start-up, and introduces liquid sulfur into the sulfur production furnace for reaction; the acid gas to be regenerated can react with the generated SO at any position at the rear part of the sulfur carrying furnace, the rear part of the waste heat boiler, the front part of the first-stage heater and the front part of the first-stage reactor2Mixing for subsequent reaction; when the acid gas is stable and the system load meets the requirement, the introduction of the liquid sulfur is stopped, and the acid gas is directly introduced into the sulfur production furnace for direct reaction, so that the device can normally produce. The method can solve the problem that the low-concentration acid gas at the initial startup stage cannot be treated and directly burned by a torch or introduced into a sulfur production furnace of a sulfur recovery device to cause high organic sulfur content SO as to influence the SO content of the flue gas2The problem of emission can be solved, and the emission of the whole sulfur device can meet the requirement of flue gas SO2The discharge is less than 100mg/m3The method ensures that the sulfur recovery device reaches the standard and discharges in the whole start-up process, is simple to operate, does not bring secondary pollution and SO2Obvious emission reduction and wide application in petroleum refining and natural productionA sulfur recovery device and a start-up process in industries such as gas purification, coal chemical industry and the like.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a flow chart of the start-up of the sulfur recovery process according to the present invention;
the reference numbers in the figures denote: 1-sulfur production furnace, 2-waste heat boiler, 3-first-stage condenser, 4-first-stage heater, 5-first-stage reactor, 6-second-stage condenser, 7-second-stage heater, 8-second-stage reactor, 9-third-stage condenser, 10-tail gas heater, 11-hydrogenation reactor, 12-steam generator, 13-quench tower, 14-absorption tower, 15-regeneration tower, 16-incinerator, 17-chimney and 18-acid gas buffer tank.
Detailed Description
As shown in the process flow and circuit diagram of FIG. 1, the sulfur recovery device of the present invention comprises an acid gas absorption pipeline (shown as circuit 1) and a sulfur recovery pipeline (shown as circuit 2); wherein the content of the first and second substances,
the acid gas absorption line (illustrated line 1) includes the following equipment:
the absorption tower 14 is used for directly introducing the acid gas generated by the upstream equipment into the absorption tower 14 for enrichment without heating treatment after liquid separation;
a regeneration tower 15 for detecting H in the amine liquid of the absorption tower 142When the concentration of S reaches a certain concentration, establishing an amine liquid circulating regeneration system by introducing a regeneration tower 15;
an incinerator 16 for absorbing acid gas and igniting the incinerator at the same time, treating tail gas, and discharging waste gas through a chimney 17;
the acid gas buffer tank 18, the acid gas regenerated by the regeneration tower 15 enters the acid gas buffer tank for temporary storage;
the sulphur recovery line (line 2 shown in the figure) comprises the following equipment:
a sulfur production furnace 1, wherein inert gas is used as power to carry liquid sulfur to the sulfur production furnace 1, air is fully combusted according to the liquid sulfur, and the liquid sulfur is enabled to produce sulfurComplete combustion in the furnace to form SO2Reacting to generate elemental sulfur and reaction furnace tail gas; controlling the temperature of a hearth of the sulfur production furnace 1 to be between 900 and 1400 ℃, preferably 1000 to 1300 ℃;
the waste heat boiler 2 is used for recovering partial heat of the generated elemental sulfur and the reaction furnace tail gas through the waste heat boiler 2;
the primary condenser 3 is used for condensing the filtered elemental sulfur and the reaction furnace tail gas in the primary condenser 3, recovering the condensed liquid sulfur, and allowing the reaction furnace tail gas to enter the subsequent reaction;
the primary heater 4 is used for heating the tail gas of the reaction furnace in the primary heater 4;
a first-stage reactor 5, wherein the first-stage reactor 5 is filled with a deoxygenation catalyst and a titanium oxide-based sulfur production catalyst; the process gas entering the primary reactor 5 can simultaneously carry out Claus reaction, organic sulfur hydrolysis reaction and SO3Carrying out reduction reaction to respectively obtain elemental sulfur and catalytic tail gas; in this example, the primary reactor 5 was filled with 1/3 volumes of the oxygen-removing catalyst in the upper part and 2/3 volumes of the titanium oxide-based sulfur-producing catalyst in the lower part. Controlling the inlet temperature of the primary reactor 5 to 200 ℃ to 250 ℃, preferably 220 ℃ to 240 ℃;
the second-stage condenser 6 is used for condensing the elemental sulfur and the catalytic tail gas which are subjected to the catalytic reaction in the first-stage reactor 5 in the second-stage condenser 6, collecting the obtained liquid sulfur, and continuously reacting the condensed catalytic tail gas;
the secondary heater 7 is used for heating the catalytic tail gas in the secondary heater 7;
the secondary reactor 8 is filled with a large-specific-surface-area alumina-based sulfur recovery catalyst, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas; controlling the inlet temperature of the secondary reactor 8 to 200 ℃ to 250 ℃, preferably 210 ℃ to 230 ℃;
the third-stage condenser 9 is used for condensing the elemental sulfur and the Claus tail gas which are subjected to the catalytic reaction in the second-stage reactor 8 in the third-stage condenser 9, collecting the obtained liquid sulfur, and continuously performing the subsequent reaction on the condensed Claus tail gas;
the tail gas heater 10 is used for heating the separated Claus tail gas entering the tail gas heater 10;
a hydrogenation reactor 11, wherein a low-temperature high-activity hydrogenation catalyst is completely filled in the hydrogenation reactor 11, and the heated Claus tail gas is used for hydrogenating and converting sulfur-containing compounds into H in the hydrogenation reactor 112S, can ensure H removal from Claus tail gas2Fully hydrogenating or hydrolyzing sulfur-containing compounds except S to obtain H2Hydrogenation tail gas of S; controlling the inlet temperature of the hydrogenation reactor to be 200-250 ℃, preferably 200-230 ℃;
a quenching tower 13 containing H2The hydrogenation tail gas of the S enters the quenching tower 13 for cooling treatment; the pH value change of the quenching tower 13 is observed at any moment in the reaction process, the pH value of the quenching tower 13 is controlled to be 7-10, and measures of ammonia injection or alkali injection are taken if necessary;
an absorption tower 14, wherein amine liquid is arranged in the absorption tower 14 and is used for absorbing H in the hydrogenation tail gas2S, further obtaining purified tail gas; controlling the top temperature of the absorption tower to be 20-38 ℃, preferably 25-35 ℃;
a regeneration tower 15 for regenerating the amine liquid and the acid gas in the absorption tower 14;
and the incinerator 16 incinerates the tail gas purified by the absorption tower 14 and discharges the tail gas through a chimney 17.
The start-up method of the sulfur recovery process shown in figure 1 specifically comprises the following steps:
(1) when the absorption tower is started, the upstream device generates acid gas and then directly introduces the acid gas into the absorption tower, namely the line 1 is opened, the line 2 is closed, the temperature of the top of the absorption tower 14 is controlled to be 25-40 ℃, preferably 25-35 ℃, the incinerator 16 is ignited at the same time, the incinerator is heated by adopting a natural gas combustion mode, the heating rate is 10-25 ℃/H, and when H in amine liquid of the absorption tower 14 is detected2When the S concentration reaches 5-8g/l, an amine liquid circulating regeneration system is established, and the regeneration is controlledThe top temperature of the raw tower 15 is 110-;
(2) when the pressure of the acid gas buffer tank 18 is detected to reach 20-40Kpa, a liquid sulfur ejector is started, inert gas is used as power to carry liquid sulfur into the sulfur production furnace 1, air is distributed according to complete combustion of the liquid sulfur, and the liquid sulfur is completely combusted in the sulfur production furnace 1 to generate SO2Post combustion SO2Mixing the acid gas with any position of the rear part of the sulfur production furnace 1, the rear part of the waste heat boiler 2, the inlet of the primary heater 4 and the inlet of the primary reactor 5 from the regeneration tower 15, and sequentially entering a subsequent reaction unit for sulfur recovery after mixing;
when the load of the acid gas reaches 10-25%, gradually reducing the amount of the acid gas introduced into the absorption tower (namely gradually closing the line 1) until the line 1 is gradually cut off, and simultaneously slowly introducing the acid gas to the sulfur production furnace 1 (namely gradually opening the line 2), adjusting the air volume according to an online instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, finishing the start-up of a sulfur recovery device, and switching to normal production;
(3) the separated reaction furnace tail gas is heated by the primary heater 4 and then enters the primary reactor 5 to perform a Claus reaction under the action of a catalyst with a selected grading, the catalytic tail gas after the reaction enters the secondary condenser 6 to be condensed, elemental sulfur is collected, the condensed catalytic tail gas is heated by the secondary heater 7 and then continues to enter the secondary reactor 8 to react, and the catalytic tail gas is subjected to Claus catalytic conversion under the action of the catalyst to generate elemental sulfur and Claus tail gas; the elemental sulfur and Claus tail gas enter the three-stage condenser 9 for condensation, the liquid sulfur generated after condensation is also collected, and the Claus tail gas (containing trace element sulfur and H) after condensation2S、SO 2And COS, CS2And the like) are heated by a tail gas heater 10, enter the hydrogenation reactor 11 and carry elemental sulfur and SO in the tail gas under the action of a hydrogenation catalyst2All of the hydrogen is converted into H2S，COS、CS2Conversion to H by hydrolysis2S; then the mixture is heated by a steam generator 12 and cooled by a quenching tower 13, and then enters an absorption tower 14 containing amine liquid, and amineLiquid absorption of H in hydrogenation tail gas2S; and the rest of the purified tail gas is introduced into an incinerator 16 and is exhausted from a chimney 17 after being incinerated, so that the requirement of a new environmental protection standard is met.
Example 1
The start-up method of a certain 15 ten thousand ton/year sulfur device is as follows: directly introducing the acid gas generated by the upstream device into the absorption tower 14, namely opening the line 1, closing the line 2, controlling the temperature at the top of the absorption tower 14 to 35 ℃, igniting the incinerator 16, heating the incinerator by adopting a natural gas combustion mode at a heating rate of 15 ℃/H, and detecting the H in the amine liquid of the absorption tower 14 when detecting the H2When the concentration of S reaches 6g/L, establishing an amine liquid circulating regeneration system, controlling the top temperature of a regeneration tower 15 to be 112 ℃, the tower kettle temperature to be 117 ℃, and feeding regenerated acid gas into an acid gas buffer tank 18; when the pressure of the buffer tank reaches 20Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into the sulfur production furnace 1, air is distributed according to complete combustion of the liquid sulfur, and the liquid sulfur is completely combusted in the sulfur production furnace to generate SO2Post combustion SO2Mixing the acid gas with the regenerated acid gas from the regeneration tower at any position of the rear part of the sulfur production furnace 1, the rear part of the waste heat boiler 2, the inlet of the primary heater 4 and the inlet of the primary reactor 5, and then sequentially entering a sulfur production unit and a tail gas treatment unit after mixing.
The subsequent sulfur production unit and the tail gas treatment unit are treated according to the conventional process, namely, the sulfur production furnace 1, the waste heat boiler 2, the primary condenser 3, the primary heater 4, the primary reactor 5, the secondary condenser 6, the secondary heater 7, the secondary reactor 8, the tertiary condenser 9, the tail gas heater 10, the hydrogenation reactor 11, the steam generator 12, the quench tower 13, the absorption tower 14 and the incinerator 16 are sequentially connected.
In the reaction process, the change of the pH value in the quenching tower 13 is observed at any moment, the pH value in the quenching tower 13 is controlled at 8, the hearth temperature of the sulfur production furnace 1 is controlled at 1250 ℃, the inlet temperature of the primary reactor 5 is controlled at 220 ℃, the inlet temperature of the secondary reactor 8 is controlled at 210 ℃, the inlet temperature of the hydrogenation reactor 11 is controlled at 220 ℃, and the top temperature of the absorption tower 14 is controlled at 35 ℃.
When the load of the acid gas reaches 10%, the acid gas amount of the acid gas introduction absorption tower is gradually reduced (the line 1 is gradually closed) and the amount of liquid sulfur introduced into the sulfur production furnace 1 is gradually reduced until the line 1 is cut off, meanwhile, the acid gas is slowly introduced into the sulfur production furnace (the line 2 is opened), the air volume is adjusted according to an online instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, the start-up of a sulfur recovery device is completed, and the normal production is switched to.
In the above embodiment of the present invention:
the deoxygenation catalyst is preferably an LS-971 catalyst developed by the research institute of the British division of petrochemical companies. LS-971 catalyst is a high Claus activity and O-leakage removing catalyst2The protective bifunctional sulfur recovery catalyst is suitable for Claus sulfur recovery devices in the fields of petrochemical industry, coal chemical industry and the like, can be used for the whole bed layer of any one-stage Claus reactor of the sulfur recovery device or be filled with other catalysts with different functions or types in a layered mode, and can generate a large amount of reaction heat in the process of removing oxygen leakage, so that the reaction temperature is increased, and the high temperature is favorable for the hydrolysis reaction of organic sulfur. Under the same device and the same process conditions, the total sulfur conversion rate can be improved by about 1 to 1.7 percent, and the method is particularly suitable for acid gas H2The sulfur recovery device with large S content or flow variation amplitude is used;
the specific surface area of the alumina-based sulfur recovery catalyst with large specific surface area is higher than 350m2Preferably LS-02 catalyst developed by the institute of Medium petrochemistry, Qilu division. The LS-02 catalyst is a novel alumina-based sulfur preparation catalyst with larger specific surface area and higher pore volume, which is developed on the basis of LS-300, and the catalyst Claus has high activity, strong heat aging resistance and hydrothermal aging resistance, uniform particles, small abrasion and high crushing strength, thereby ensuring the long-period operation of the catalyst; more reasonable pore structure, more macropores and bimodal distribution of pore structure, so that the sulfur generated by reaction can quickly leave the pore channel of the catalyst, and the Claus activity and the organic sulfur hydrolytic activity of the catalyst are further improved.
The low-temperature oxygen-resistant high-activity hydrogenation catalyst is preferably an LSH-03A catalyst developed by the research institute of the Qilu petrochemical division, the inlet temperature of a hydrogenation reactor using the catalyst can be controlled to be 220-260 ℃, the activity of the catalyst is improved by more than 30 percent compared with that of a common catalyst, the catalyst has excellent low-temperature hydrogenation and hydrolysis activity, and the content of organic sulfur in hydrogenation tail gas can be ensured to be lower than 20 ppm.
The catalyst of the invention can be purchased from the market, and the physicochemical properties and technical indexes of the catalyst are shown in the following table 1.
TABLE 1 physicochemical Properties and technical indices of the catalysts
| Physicochemical Properties | LS-971 | LS-02 | LSH-03A |
| Appearance of the product | Reddish brown spherical | White sphere | Grey green clover strip |
| Specification/mm | Φ3～Φ5 | Φ4～6 | Φ3×5-10 |
| strength/N.cm-1 | ≥140 | Not less than 120N/granule | ≥200 |
| Abrasion, (m/m)% | ≤0.5 | ≤0.5 | ≤0.5 |
| Bulk density/kg. L-1 | 0.75～0.85 | 0.65-0.72 | 0.7-0.8 |
| Specific surface area/m2·g-1 | ≥220 | ≥350 | ≥180 |
| Pore volume/mL. g-1 | ≥0.35 | ≥0.45 | ≥0.35 |
| Principal Components | Al2O3+Fe2O3 | Al2O3 | CoO+MoO3+Al2O3 |
Comparative example 1
The sulfur recovery process of this comparative example differs from the process of example 1 only in that the acid gas produced in the upstream plant is introduced directly into the sulfur production furnace 1 for treatment in a conventional manner according to the conventional Claus + SCOT process, i.e., the step in which the acid gas is introduced directly into the absorption tower for treatment during the process is omitted.
Compared with the traditional Claus + SCOT process in the comparative example 1, the process in the embodiment 1 of the invention solves the problems that the acid gas is directly discharged to the torch in the starting process, and the like, and the process of the invention is adopted for starting and running periodIntermittent flue gas SO2Are all less than 80mg/m3And meets the latest environmental protection requirement.
Example 2
The start-up method of a certain 8 ten thousand ton/year sulfur device is as follows: directly introducing acid gas generated by an upstream device into an absorption tower, opening a line 1, closing a line 2, controlling the temperature of the top of the absorption tower to 25 ℃, igniting an incinerator, heating the incinerator by adopting a natural gas combustion mode at a heating rate of 10 ℃/H, and detecting H in amine liquid of the absorption tower2When the concentration of S reaches 8g/L, establishing an amine liquid circulating regeneration system, controlling the temperature of the top of a regeneration tower to be 115 ℃, controlling the temperature of a tower kettle to be 120 ℃, and feeding regenerated acid gas into an acid gas buffer tank; when the pressure of the buffer tank reaches 40Kpa, the liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into the sulfur production furnace, air is distributed according to the complete combustion of the liquid sulfur, and the liquid sulfur is completely combusted in the sulfur production furnace to generate SO2Post combustion SO2Mixing the acid gas with the regenerated acid gas from the regeneration tower at any position of the rear part of the sulfur production furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and then sequentially entering a sulfur production unit and a tail gas treatment unit after mixing.
In the reaction process, the change of the pH value in the quenching tower 13 is observed at any moment, the pH value in the quenching tower 13 is controlled at 7, and the temperature of a hearth of the sulfur production furnace 1 is controlled to be 1180 ℃, the temperature of an inlet of the primary reactor 5 is controlled to be 240 ℃, the temperature of an inlet of the secondary reactor 8 is controlled to be 220 ℃, the temperature of an inlet of the hydrogenation reactor 11 is controlled to be 230 ℃, and the temperature of the top of the absorption tower 14 is controlled to be 25 ℃.
When the load of the acid gas reaches 25%, the acid gas amount of the acid gas introduction absorption tower is gradually reduced (the line 1 is gradually closed) and the amount of liquid sulfur introduced into the sulfur production furnace is gradually reduced until the line 1 is cut off, meanwhile, the acid gas is slowly introduced into the sulfur production furnace (the line 2 is opened), the air volume is adjusted according to an on-line instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, the start-up of a sulfur recovery device is completed, and the normal production is switched to.
Comparative example 2
The sulfur recovery process of this comparative example differs from the process of example 2 only in that the acid gas produced in the upstream plant is introduced directly into the sulfur production furnace 1 for treatment in a conventional manner according to the conventional Claus + SCOT process, i.e., the step in which the acid gas is introduced directly into the absorption tower for treatment during the process is omitted.
Compared with the traditional Claus + SCOT process in the comparative example 2, the process in the embodiment 2 of the invention solves the problems that the acid gas is directly discharged to the torch in the starting process, and the like, and the flue gas SO is generated during the starting and running process of the process2Are all less than 60mg/m3And meets the latest environmental protection requirement.
Example 3
The start-up method of a certain 10 ten thousand ton/year sulfur device is as follows: directly introducing the acid gas generated by the upstream device into the absorption tower, namely opening the line 1, closing the line 2, controlling the temperature of the top of the absorption tower to be 30 ℃, igniting the incinerator, heating the incinerator by adopting a natural gas combustion mode at a heating rate of 25 ℃/H, and detecting H in the amine liquid of the absorption tower2When the concentration of S reaches 5g/L, establishing an amine liquid circulating regeneration system, controlling the temperature of the top of a regeneration tower to be 110 ℃, the temperature of a tower kettle to be 115 ℃, and feeding regenerated acid gas into an acid gas buffer tank; when the pressure of the buffer tank reaches 35Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into the sulfur production furnace, air is distributed according to complete combustion of the liquid sulfur, and the liquid sulfur is completely combusted in the sulfur production furnace to generate SO2Post combustion SO2Mixing the acid gas with the regenerated acid gas from the regeneration tower at any position of the rear part of the sulfur production furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and then sequentially entering a sulfur production unit and a tail gas treatment unit after mixing.
In the reaction process, the change of the pH value in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 9, and the hearth temperature of the sulfur production furnace 1 is controlled at 1310 ℃, the inlet temperature of the primary reactor 5 is controlled at 230 ℃, the inlet temperature of the secondary reactor 8 is controlled at 212 ℃, the inlet temperature of the hydrogenation reactor 11 is controlled at 233 ℃, and the top temperature of the absorption tower 14 is controlled at 30 ℃.
When the load of the acid gas reaches 15%, gradually reducing the acid gas amount of the acid gas introduction absorption tower (gradually closing the line 1) and the amount of liquid sulfur to the sulfur production furnace until the line 1 is cut off, simultaneously slowly introducing the acid gas to the sulfur production furnace (opening the line 2), adjusting the air volume according to an on-line instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, finishing the start-up of the sulfur recovery device, and switching to normal production.
Comparative example 3
The sulfur recovery process of this comparative example differs from the process of example 3 only in that the acid gas produced in the upstream plant is introduced directly into the sulfur production furnace 1 for treatment in a conventional manner according to the conventional Claus + SCOT process, i.e., the step in which the acid gas is introduced directly into the absorption tower for treatment during the process is omitted.
Compared with the traditional Claus + SCOT process in the comparative example 3, the process in the embodiment 3 of the invention solves the problems that the acid gas is directly discharged to the torch in the starting process, and the like, and the flue gas SO is generated during the starting and running process by adopting the process2Are all less than 70mg/m3And meets the latest environmental protection requirement.
Example 4
The start-up method of a certain 4 ten thousand ton/year sulfur device is as follows: directly introducing the acid gas generated by the upstream device into the absorption tower, namely opening the line 1, closing the line 2, controlling the temperature of the top of the absorption tower to 32 ℃, igniting the incinerator, heating the incinerator by adopting a natural gas combustion mode at the heating rate of 12 ℃/H, and detecting H in the amine liquid of the absorption tower2When the concentration of S reaches 7g/L, establishing an amine liquid circulating regeneration system, controlling the temperature of the top of the regeneration tower to be 113 ℃, the temperature of a tower kettle to be 117 ℃, feeding regenerated acid gas into an acid gas buffer tank, starting a liquid sulfur injector when the pressure of the buffer tank reaches 26Kpa, feeding inert gas as power to carry liquid sulfur into a sulfur production furnace, and completely combusting the liquid sulfur according to the liquid sulfur to distribute air SO that the liquid sulfur is completely combusted in the sulfur production furnace to generate SO2Post combustion SO2Mixing the acid gas with the regenerated acid gas from the regeneration tower at any position of the rear part of the sulfur production furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and then sequentially entering a sulfur production unit and a tail gas treatment unit after mixing.
In the reaction process, the change of the pH value in the quenching tower 13 is observed at any moment, the pH value in the quenching tower 13 is controlled to be 8, and measures of ammonia injection or alkali injection are taken if necessary; and controlling the hearth temperature of the sulfur production furnace 1 to be 1225 ℃, the inlet temperature of the primary reactor 5 to be 228 ℃, the inlet temperature of the secondary reactor 8 to be 218 ℃, the inlet temperature of the hydrogenation reactor 11 to be 235 ℃ and the top temperature of the absorption tower 14 to be 32 ℃.
When the load of the acid gas reaches 13%, gradually reducing the acid gas amount of the acid gas introduction absorption tower (gradually closing the line 1) and the amount of liquid sulfur to the sulfur production furnace until the line 1 is cut off, simultaneously slowly introducing the acid gas to the sulfur production furnace (opening the line 2), adjusting the air volume according to an on-line instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, finishing the start-up of the sulfur recovery device, and switching to normal production.
Comparative example 4
The sulfur recovery process of this comparative example differs from the process of example 4 only in that the acid gas produced in the upstream plant is introduced directly into the sulfur production furnace 1 for treatment in a conventional manner according to the conventional Claus + SCOT process, i.e., the step in which the acid gas is introduced directly into the absorption tower for treatment during the process is omitted.
Compared with the traditional Claus + SCOT process in the comparative example 4, the process in the embodiment 4 of the invention solves the problems that the acid gas is directly discharged to the torch in the starting process, and the like, and the flue gas SO is generated during the starting and running process of the process2Are all less than 55mg/m3And meets the latest environmental protection requirement.
Example 5
The start-up method of a certain 7 ten thousand ton/year sulfur device is as follows: directly introducing the acid gas generated by the upstream device into the absorption tower, namely opening the line 1, closing the line 2, controlling the temperature of the top of the absorption tower to be 28 ℃, igniting the incinerator, heating the incinerator by adopting a natural gas combustion mode at a heating rate of 16 ℃/H, and detecting H in the amine liquid of the absorption tower2When the concentration of S reaches 5g/l, establishing an amine liquid circulating regeneration system, controlling the temperature of the top of a regeneration tower to be 114 ℃, the temperature of a tower kettle to be 118 ℃, feeding regenerated acid gas into an acid gas buffer tank, starting a liquid sulfur injector when the pressure of the buffer tank reaches 31Kpa, feeding inert gas as power to carry liquid sulfur into a sulfur production furnace, and completely combusting the liquid sulfur according to the liquid sulfur to distribute air SO that the liquid sulfur is completely combusted in the sulfur production furnace to generate SO2Post combustion SO2Mixing the acid gas with the regenerated acid gas from the regeneration tower at any position of the rear part of the sulfur production furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and then sequentially entering a sulfur production unit and a tail gas treatment unit after mixing.
In the reaction process, the change of the pH value in the quenching tower 13 is observed at any moment, the pH value in the quenching tower 13 is controlled to be 9, and measures of ammonia injection or alkali injection are taken if necessary; and controlling the hearth temperature of the sulfur production furnace 1 to 1160 ℃, the inlet temperature of the primary reactor 5 to 225 ℃, the inlet temperature of the secondary reactor 8 to 221 ℃, the inlet temperature of the hydrogenation reactor 11 to 235 ℃ and the top temperature of the absorption tower 14 to 28 ℃.
When the load of the acid gas reaches 12%, gradually reducing the acid gas amount of the acid gas introduction absorption tower (gradually closing the line 1) and the amount of liquid sulfur to the sulfur production furnace until the line 1 is cut off, simultaneously slowly introducing the acid gas to the sulfur production furnace (opening the line 2), adjusting the air volume according to an on-line instrument, the temperature of a hearth of the sulfur production furnace, the temperature of a reactor and the like, finishing the start-up of the sulfur recovery device, and switching to normal production.
Comparative example 5
The sulfur recovery process of this comparative example differs from the process of example 5 only in that the acid gas produced in the upstream plant is introduced directly into the sulfur production furnace 1 for treatment in a conventional manner in accordance with the conventional Claus + SCOT process, i.e., the step in which the acid gas is introduced directly into the absorption tower for treatment during the process is omitted.
Compared with the traditional Claus + SCOT process in the comparative example 5, the process in the embodiment 5 of the invention solves the problems that the acid gas is directly discharged to the torch in the starting process, and the like, and the flue gas SO is generated during the starting and running process of the process2Are all less than 90mg/m3And meets the latest environmental protection requirement.
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 therefrom are within the scope of the invention.
Claims (10)
1. The sulfur recovery process starting method is characterized by comprising the following steps:
(1) at the initial stage of start-up, directly introducing the acidic gas generated by upstream device into absorption tower to make enrichment absorption, when it is detectedMeasuring H in absorption tower2When the concentration of S reaches a preset value, starting a regeneration tower to perform amine liquid cyclic regeneration treatment, and collecting the regenerated acid gas for later use;
(2) inputting the liquid sulfur to be treated into a sulfur production furnace, and completely combusting the liquid sulfur according to air distribution to generate SO2；
(3) SO after combustion2Mixing with the regenerated acid gas, performing Claus reaction, and condensing and recovering the obtained liquid sulfur; the produced Claus tail gas is subjected to hydrogenation reaction treatment to carry out tail gas treatment.
2. The start-up method of the sulfur recovery process according to claim 1, wherein the step (1) further comprises the step of starting an incinerator for acid gas regeneration tail gas treatment, and the temperature rise rate of the incinerator is controlled to be 10-25 ℃/h.
3. The start-up method of sulfur recovery process according to claim 1 or 2, wherein in the step (1), H in the amine liquid of the absorption tower is controlled2And when the S reaches 5-8g/L, starting the regeneration tower.
4. The sulfur recovery process start-up method according to any one of claims 1 to 3, wherein in the step (1), the temperature of the absorption tower is controlled to be 20 ℃ to 40 ℃, the tower top temperature of the regeneration tower is controlled to be 110-.
5. The sulfur recovery process starting method according to any one of claims 1 to 4, wherein in the step (2), when the acid gas is stable and the system load meets the requirement, the gas amount introduced into the absorption tower by the acid gas is gradually reduced, and the acid gas generated by an upstream device is slowly introduced into the sulfur production furnace until the sulfur recovery device is started and normal production is carried out.
6. The sulfur recovery process starting method according to any one of claims 1 to 5, wherein in the step (2), the liquid sulfur is carried into the sulfur production furnace by taking inert gas as power, and the temperature of the inert gas is controlled to be 120 ℃ and 140 ℃.
7. The process for operating a sulfur recovery process according to any one of claims 1 to 6, wherein in step (3), the SO after combustion is used2And the regenerated acid gas is mixed at any position between the rear part of the sulfur production furnace and the inlet of the Claus reactor.
8. The process for starting up a sulphur recovery process according to any one of claims 1 to 7, wherein in step (3);
the catalyst of the claus reaction treatment step comprises a claus catalyst;
the temperature of the claus reaction step is between 200 ℃ and 250 ℃.
9. The process for operating a sulfur recovery process according to any one of claims 1 to 8, wherein in the step (3):
the catalyst in the hydrogenation reaction treatment step comprises a pre-vulcanized Claus tail gas hydrogenation catalyst, an oxidation state Claus tail gas hydrogenation catalyst or a vulcanized oxidation state Claus tail gas hydrogenation catalyst;
the temperature of the hydrogenation step is 200-250 ℃.
10. The sulfur recovery process starting method according to any one of claims 1 to 9, wherein in the step (3), the tail gas treatment step comprises a step of introducing tail gas into the absorption tower and a step of introducing the tail gas into the regeneration tower for regeneration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010624168.5A CN113860266B (en) | 2020-06-30 | 2020-06-30 | Method for starting sulfur recovery process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010624168.5A CN113860266B (en) | 2020-06-30 | 2020-06-30 | Method for starting sulfur recovery process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113860266A true CN113860266A (en) | 2021-12-31 |
| CN113860266B CN113860266B (en) | 2023-06-16 |
Family
ID=78982036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010624168.5A Active CN113860266B (en) | 2020-06-30 | 2020-06-30 | Method for starting sulfur recovery process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113860266B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482532A (en) * | 1983-07-29 | 1984-11-13 | Standard Oil Company (Indiana) | System and process for producing elemental sulfur |
| US20110171115A1 (en) * | 2009-07-22 | 2011-07-14 | Kps Technology & Engineering Llc | Method and Consolidated Apparatus for Recovery of Sulfur from Acid Gases |
| CN102838088A (en) * | 2012-09-18 | 2012-12-26 | 中国石油集团工程设计有限责任公司 | Integrated sour gas treating process |
| CN104249996A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Technology for reducing SO2 emission concentration of sulfur recovery apparatus |
| CN105129741A (en) * | 2014-06-06 | 2015-12-09 | 中国石油化工股份有限公司 | Process for reducing SO2 emission concentration of sulfur recovery device |
| CN105819404A (en) * | 2016-03-15 | 2016-08-03 | 山东三维石化工程股份有限公司 | Zero-discharge startup and shutdown technology of sulfur recovering device |
| CN107537297A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The flue gas circulation desulfuration technique of clean environment firendly |
| US20180065851A1 (en) * | 2016-09-03 | 2018-03-08 | Mahin Rameshni | Setr- super enhanced tail gas recovery; a tail gas process with adsorbent reactors for zero emissions |
| CN209173684U (en) * | 2018-10-24 | 2019-07-30 | 中国石油化工股份有限公司 | Hot nitrogen purges sulphur unit |
-
2020
- 2020-06-30 CN CN202010624168.5A patent/CN113860266B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482532A (en) * | 1983-07-29 | 1984-11-13 | Standard Oil Company (Indiana) | System and process for producing elemental sulfur |
| US20110171115A1 (en) * | 2009-07-22 | 2011-07-14 | Kps Technology & Engineering Llc | Method and Consolidated Apparatus for Recovery of Sulfur from Acid Gases |
| CN102838088A (en) * | 2012-09-18 | 2012-12-26 | 中国石油集团工程设计有限责任公司 | Integrated sour gas treating process |
| CN104249996A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Technology for reducing SO2 emission concentration of sulfur recovery apparatus |
| CN105129741A (en) * | 2014-06-06 | 2015-12-09 | 中国石油化工股份有限公司 | Process for reducing SO2 emission concentration of sulfur recovery device |
| CN105819404A (en) * | 2016-03-15 | 2016-08-03 | 山东三维石化工程股份有限公司 | Zero-discharge startup and shutdown technology of sulfur recovering device |
| CN107537297A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The flue gas circulation desulfuration technique of clean environment firendly |
| US20180065851A1 (en) * | 2016-09-03 | 2018-03-08 | Mahin Rameshni | Setr- super enhanced tail gas recovery; a tail gas process with adsorbent reactors for zero emissions |
| CN209173684U (en) * | 2018-10-24 | 2019-07-30 | 中国石油化工股份有限公司 | Hot nitrogen purges sulphur unit |
Non-Patent Citations (3)
| Title |
|---|
| S. IBRAHIM ET AL: "Role of toluene to acid gas(H2S and CO2) combustion in H2/O2-N2 flame under Claus condition:", 《APPLIED ENERGY》 * |
| 向虹: "240 kt/a硫磺回收装置运行探讨", 《硫酸工业》 * |
| 郭宏,张松平: "还原吸收再循环硫磺回收及尾气处理工艺的工业应用" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113860266B (en) | 2023-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8871176B2 (en) | Process for reducing sulfur emission of sulfur plant | |
| CN102910593B (en) | System and method for treating waste acid gas | |
| CN103939918B (en) | Incineration method for acid gas and liquid purification | |
| CN103822217B (en) | A kind of sour gas pretreatment technology | |
| AU2019303489B2 (en) | Acid gas treatment | |
| US20180065851A1 (en) | Setr- super enhanced tail gas recovery; a tail gas process with adsorbent reactors for zero emissions | |
| CN104249995A (en) | Method for reducing SO2 emission concentration of sulfur recovery device | |
| CN206127222U (en) | A manufacturing equipment for following tar stock is produced through purified hydrocarbon | |
| CN106219499A (en) | Desulfurization and sulfur recovery technology | |
| AU2018201480A1 (en) | Improved sulphur dioxide treatment | |
| CN101193690A (en) | Treatment of fuel gas | |
| CN210973883U (en) | Sulfur recovery device is blown in circulation | |
| EP3597286A1 (en) | Acid gas treatment | |
| CN104249996A (en) | Technology for reducing SO2 emission concentration of sulfur recovery apparatus | |
| CN108704474A (en) | Coke oven flue gas and Claus tail gases combined treatment process | |
| CN108178132B (en) | Sulfur recovery method and equipment in carbon disulfide production | |
| CN113860266B (en) | Method for starting sulfur recovery process | |
| CN202864918U (en) | Waste gas treatment system of acid gas | |
| McIntyre et al. | Claus sulphur recovery options | |
| CN103906558B (en) | The fractional combustion of the flammable effluent of the sulfur-bearing of recyclable sulphur in CLAUS method | |
| JP2003534897A (en) | Method and apparatus for regenerating spent absorbent generated in heat generator flue gas treatment | |
| CN114774611A (en) | Hydrogen rich gas CO2Method for producing iron by oxidation conversion and hydrogen-based shaft furnace direct reduction | |
| CN112648628A (en) | Ultralow-sulfur emission process for flue gas of sulfur recovery device | |
| CN113860265B (en) | System and process for preparing sulfur by efficiently treating alkylated waste acid | |
| CN113860267B (en) | System and process for preparing sulfur by efficiently treating alkylated waste acid |
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 |