CN113860266B - Method for starting sulfur recovery process - Google Patents
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- CN113860266B CN113860266B CN202010624168.5A CN202010624168A CN113860266B CN 113860266 B CN113860266 B CN 113860266B CN 202010624168 A CN202010624168 A CN 202010624168A CN 113860266 B CN113860266 B CN 113860266B
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- B01D53/34—Chemical or biological purification of waste gases
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- 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
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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Abstract
The invention belongs to the technical field of sulfur recovery, and particularly relates to a startup method of a sulfur recovery process. According to the method for starting the sulfur recovery process, acid gas is introduced into the absorption tower for enrichment absorption and regeneration during starting, and liquid sulfur is introduced into the sulfur production furnace for reaction; the acid gas after regeneration can be reacted with SO at any position at the rear part of the sulfur furnace, the rear part of the waste heat boiler, the front part of the primary heater and the front part of the primary reactor 2 Mixing to carry out 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 producing furnace for direct reaction, so that the device can normally produce. The method can solve the problem that the low-concentration acid gas cannot be treated in the initial stage of starting work, and the organic sulfur content is high SO as to influence the SO of the flue gas caused by directly burning by a torch or introducing the low-concentration acid gas into a sulfur producing furnace of a sulfur recovery device 2 The problem of emission ensures that the sulfur recovery device reaches the standard 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 start-up method which is suitable for the sulfur recovery process start-up process in petroleum refining, coal chemical industry and natural gas purification industries, and is particularly suitable for low acid gas concentration in the initial start-up period.
Background
Sulfide in crude oil or coal is converted into highly toxic substance H in the processing process 2 S, the sulfur recovery process has great toxic effect on human bodies and the environment, and the sulfur recovery process is the most suitable process adopted correspondingly, wherein harmless treatment is needed. Sulfur recovery refers to a chemical process of converting sulfides in toxic sulfur-containing gases containing hydrogen sulfide and the like into elemental sulfur, thereby changing waste into valuables and protecting the environment. In a chemical plant using coal as a raw material, the processing and recycling flow of the acid gas mainly comprises coal, coal chemical industry, desulfurization, H2S, sulfur recycling and sulfur.
At present, the sulfur recovery technology mainly comprises a Claus+SCOT process, a super/super-optimal Claus process, a Lo-Cat process and the like. Among them, claus+SCOT technology is widely used because of the characteristics of high sulfur recovery rate, wide application range and the like. The Claus+SCOT process is that the acid gas is combusted in a combustion furnace, wherein NH 3 And the hydrocarbon component is completely oxidatively decomposed, while H 2 S is incompletely combusted, about 60-65% is directly converted into elemental sulfur, and the rest is H 2 S is also converted into SO by 1/3 2 ，H 2 S and SO 2 The low-temperature Claus reaction is carried out under the condition of catalyst, the sulfur conversion rate reaches more than 97 percent, and the residual H 2 S and SO 2 And S which is not trapped is subjected to hydrogenation reduction and absorption and regeneration, so that the sulfur yield of the device reaches more than 99.9 percent. According to the different concentration of the treated acid gas, the Claus process is divided into a direct current method and a split-flow method, wherein the acid gas with the treatment concentration of 50-100% is generally treated by the direct current methodThe method for preheating the acid gas and the air is generally adopted for 30-50% of the acid gas, the method for splitting the acid gas with the concentration of 15-30% is generally adopted for treating the acid gas with the concentration of 5-15% is generally adopted for splitting the preheated acid gas and the air, and the fuel gas is properly mixed and burned.
According to the specification of the emission standard GB31570-2015 of pollutants in petroleum refining industry, the limit value of the emission concentration of the atmospheric pollutants of a sulfur recovery device, namely sulfur dioxide, is less than 400mg/Nm 3 Standard, in particular regional execution of less than 100mg/Nm 3 . But the provision does not start and stop the sulfur recovery plant for flue gas SO 2 The emission concentration is regulated, so that if the requirements of the emission standard GB31570-2015 of pollutants in petroleum refining industry are met during the start-up and shutdown period, the sulfur recovery device during the start-up and shutdown period is a great test. Because the concentration of the acid gas is low in the beginning of operation, when the sulfur plant is introduced, the load of the plant is low, and the sulfur producing furnace cannot keep stable flame. Therefore, more methods are adopted at present to directly burn off the discharge torch, but the method causes huge environmental pollution. The other method which is currently feasible is to adopt gas or natural gas for supporting combustion, the air distribution is greatly influenced by factors such as flowmeter and composition change, but carbon deposition is extremely easy to cause deactivation of the catalyst, increase of bed pressure drop and the like to be forced to stop; at the same time, a great deal of CO is generated in the sulfur producer due to the introduction of natural gas and gas 2 And CO 2 The existence of the catalyst can cause a plurality of side reactions, and a large amount of organic sulfur is generated in the sulfur-producing furnace, which brings burden to the subsequent catalyst and affects the SO of the flue gas of the device 2 And (5) discharging.
For example, chinese patent CN105819404a discloses a zero-discharge start-stop process for sulfur recovery device, and the start-up method comprises: (1) during the start-up baking, the baking flue gas directly enters an alkali liquor absorption tower; (2) during the temperature rising period of the converter, the tail gas from the tail gas liquid separating tank enters the incinerator for incineration, and the obtained high-temperature flue gas is fed into the alkali liquor absorption tower after the waste heat is recovered by the tail gas waste heat boiler; (3) during the presulfiding of the hydrogenation reactor catalyst, the concentration of the catalyst in the hydrogenation reactor is controlled by a ratio analyzer by using hydrogen sulfide in the sulfur production process gas, and the hydrogenated tail gas is introduced into an incinerator for incineration from the front of a quenching towerThen the SO is absorbed by an alkali liquor absorption tower 2 . However, the method belongs to the post-alkaline washing process, has high construction and operation cost and serious corrosion, and can simultaneously generate waste alkali liquor to form new pollution.
As another example, chinese patent CN202829575U discloses a sulfur recovery device, in which raw acid gas is introduced into a hydrogenation reactor to perform presulfiding of a hydrogenation catalyst while the whole sulfur recovery device is started to heat up in a furnace at a start-up point, so as to realize synchronous start-up of a claus unit and a tail gas purification unit. However, the device still fails to handle the low concentration acid gas of initial stage of beginning of a job, and introduces tail gas hydrogenation unit process at some stove and claus unit process gas and easily causes tail gas emission to exceed standard to easily cause the catalyst to fly the temperature in the period of beginning of a job, can not satisfy whole beginning of a job process emission up to standard, especially in initial stage of beginning of a job, still has the unable defect of handling of low concentration acid gas.
Therefore, it is necessary to develop a sulfur recovery process which can sufficiently solve the above-mentioned problems, particularly in the treatment of low-concentration acid gas at the beginning of the start-up.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for starting the sulfur recovery process, which can solve the problem that the low-concentration acid gas cannot be treated at the beginning of the starting process, and the sulfur recovery device is directly burnt by a torch or introduced into a sulfur producing furnace to produce sulfur, SO that the content of organic sulfur is high, and the SO of flue gas is influenced 2 The emission problem is to ensure that the sulfur recovery device reaches the emission standard in the whole start-up process, the operation is simple, no secondary pollution is caused, and SO 2 Obvious emission reduction, and can be widely applied to sulfur recovery devices and startup processes in industries such as petroleum refining, natural gas purification, coal chemical industry and the like.
In order to solve the technical problems, the method for starting the sulfur recovery process comprises the following steps:
(1) In the initial stage of starting operation, the acid gas produced by the upstream device is directly introduced into an absorption tower for enrichment absorption, and when H in the absorption tower is detected 2 When the S concentration reaches a preset value, starting a regeneration tower to perform amine liquid circulation regeneration treatment, and collecting the regenerated acid gas for later use;
(2) The liquid sulfur to be treated is input into a sulfur producing furnace, and is completely combusted according to the liquid sulfur to be distributed with air, SO that the liquid sulfur is completely combusted in the sulfur producing furnace to generate SO 2 ；
(3) SO after combustion 2 Mixing with the regenerated acid gas, carrying out a Claus reaction, and condensing and recycling the obtained liquid sulfur; the generated Claus tail gas is subjected to hydrogenation treatment to carry out tail gas treatment.
Specifically, in the step (1), the acid gas is directly introduced into the absorption tower without heating after being separated.
Specifically, in the step (1), the method further comprises the step of starting the incinerator to conduct acid gas regeneration tail gas treatment, the heating rate of the incinerator is controlled to be 10-25 ℃/h, and preferably the incinerator is 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 controlled 2 And when 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 ℃, preferably 25-35 ℃; controlling the tower top temperature of the regeneration tower to be 110-115 ℃ and the tower bottom temperature to be 115-120 ℃.
Specifically, in the step (2), when the acid gas is stable and the system load meets the requirement, gradually reducing the gas quantity of the acid gas introduced into the absorption tower, and slowly introducing the acid gas generated by an upstream device into the sulfur-making furnace until the sulfur recovery device is started up, and turning into normal production.
Specifically, in the step (2), inert gas is used as power to carry the liquid sulfur into the sulfur producing furnace, and the temperature of the inert gas is controlled to be 120-140 ℃. The inert gas can be nitrogen, or absorbing tower top purified gas or flue gas after the incinerator. The acid gas is slowly led into the sulfur producing furnace, and concretely, the acid gas can be preheated or not; the acid gas can enter the sulfur producing furnace by adopting a direct current method process or a split flow method.
Specifically, in the step (2), the air distribution according to the complete combustion of the liquid sulfur disclosed by the invention specifically refers to the air distribution (air) entering the sulfur making furnace, and the air distribution can be preheated or not.
Specifically, in the step (3), the burnt SO 2 Is mixed with the regenerated acid gas at any position between the rear of the sulfur producing furnace and the inlet of the claus reactor. In particular to the rear part of the sulfur producing furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, which can be mixed in a single way or in multiple ways, and then sequentially enter the sulfur producing unit and the tail gas treatment unit.
Preferably, the furnace chamber temperature of the sulfur producing furnace is controlled between 900 ℃ and 1400 ℃, preferably 1000 ℃ to 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, titanium oxide-based sulfur production catalyst, oxygen leakage removal catalyst and the like, and can be graded at will or filled completely. Preferably, in the first-stage reactor, the upper part is filled with 1/3 volume of oxygen-removing catalyst, and the lower part is filled with 2/3 volume of titanium oxide-based sulfur-producing catalyst.
The temperature of the claus reaction step is 200-250 ℃.
Specifically, in the step (3):
the catalyst of the hydrogenation treatment step comprises a pre-sulfided claus tail gas hydrogenation catalyst, an oxidized claus tail gas hydrogenation catalyst or a sulfided oxidized claus tail gas hydrogenation catalyst;
the temperature of the hydrogenation reaction 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 hydrotreating step specifically means that the space velocity of the hydrogenation reactor is controlled to be 200 hours -1 -1000h -1 Preferably airspeed controlIs made into 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 gas-gas heat exchange, high-temperature blending, electric heating, heating furnaces and other processes.
According to the method for starting the sulfur recovery process, acid gas is introduced into the absorption tower for enrichment absorption and regeneration during starting, and liquid sulfur is introduced into the sulfur production furnace for reaction; the acid gas after regeneration can be reacted with SO at any position at the rear part of the sulfur furnace, the rear part of the waste heat boiler, the front part of the primary heater and the front part of the primary reactor 2 Mixing to carry out 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 producing furnace for direct reaction, so that the device can normally produce. The method can solve the problem that the low-concentration acid gas cannot be treated in the initial stage of starting work, and the organic sulfur content is high SO as to influence the SO of the flue gas caused by directly burning by a torch or introducing the low-concentration acid gas into a sulfur producing furnace of a sulfur recovery device 2 The emission problem can be solved, and the emission of the whole sulfur device can meet the SO of flue gas 2 The discharge is less than 100mg/m 3 The aim of the method is to ensure that the sulfur recovery device reaches the standard and is discharged in the whole start-up process, the operation is simple, no secondary pollution is caused, and SO is produced 2 Obvious emission reduction, and can be widely applied to sulfur recovery devices and startup processes in industries such as petroleum refining, natural gas purification, coal chemical industry and the like.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a flow chart of the sulfur recovery process of the invention;
the reference numerals in the drawings are as follows: 1-sulfur making furnace, 2-waste heat boiler, 3-primary condenser, 4-primary heater, 5-primary reactor, 6-secondary condenser, 7-secondary heater, 8-secondary reactor, 9-tertiary condenser, 10-tail gas heater, 11-hydrogenation reactor, 12-steam generator, 13-quench tower, 14-absorption tower, 15-regeneration tower, 16-incinerator, 17-chimney, 18-acid gas buffer tank.
Detailed Description
As shown in the process flow and the circuit diagram of fig. 1, the sulfur recovery device of the invention comprises an acid gas absorption pipeline (shown as a circuit 1) and a sulfur recovery pipeline (shown as a circuit 2); wherein, the liquid crystal display device comprises a liquid crystal display device,
the acid gas absorption line (illustrated line 1) comprises the following equipment:
the acid gas generated by upstream equipment of the absorption tower 14 can be directly introduced into the absorption tower 14 for enrichment without heating treatment after being separated;
a regeneration tower 15 for detecting H in the amine liquid of the absorption tower 14 2 When the S concentration reaches a certain concentration, an amine liquid circulating regeneration system is established by introducing the S into the regeneration tower 15;
the incinerator 16 is ignited while absorbing acid gas, the tail gas is treated, and the waste gas is discharged through a chimney 17;
an acid gas buffer tank 18, into which the acid gas regenerated by the regeneration tower 15 is temporarily stored;
the sulfur recovery line (illustrated line 2) comprises the following equipment:
the sulfur producing furnace 1 carries liquid sulfur by taking inert gas as power to carry out the inside of the sulfur producing furnace 1, and the air distribution is carried out according to the complete combustion of the liquid sulfur, SO that the liquid sulfur is completely combusted in the sulfur producing furnace to generate SO 2 Reacting to generate elemental sulfur and reaction furnace tail gas; the hearth temperature of the sulfur producing furnace 1 is controlled to be 900-1400 ℃, preferably 1000-1300 ℃;
a waste heat boiler 2, wherein part of heat is recovered from the generated elemental sulfur and the tail gas of the reaction furnace through the waste heat boiler 2;
the primary condenser 3 is used for condensing the element sulfur and the tail gas of the reaction furnace which are subjected to filtration treatment, wherein the liquid sulfur obtained by condensation is recovered, and the tail gas of the reaction furnace is subjected to subsequent reaction;
a primary heater 4, wherein the tail gas of the reaction furnace is heated in the primary heater 4;
a primary reactor 5, wherein the primary reactor 5 is filled with oxygen leakage removal catalystA catalyst for preparing sulfur by using a catalyst and titanium oxide; the process gas entering the primary reactor 5 can be subjected to the claus reaction, the organosulfur hydrolysis reaction and the SO simultaneously 3 The reduction reaction is carried out to obtain elemental sulfur and catalytic tail gas respectively; in this example, the upper part of the primary reactor 5 is filled with 1/3 volume of oxygen-removing catalyst, and the lower part is filled with 2/3 volume of titanium oxide-based sulfur-producing catalyst. Controlling the inlet temperature of the primary reactor 5 to be 200-250 ℃, preferably 220-240 ℃;
the second-stage condenser 6 is used for condensing elemental sulfur and catalytic tail gas after catalytic reaction in the first-stage reactor 5, the obtained liquid sulfur is collected, and the condensed catalytic tail gas is reacted continuously;
a secondary heater 7, wherein the catalytic tail gas is heated in the secondary heater 7;
the secondary reactor 8 is filled with alumina-based sulfur recovery catalyst with large specific surface area, 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 be 200-250 ℃, preferably 210-230 ℃;
the tertiary condenser 9 is used for condensing elemental sulfur and Claus tail gas after catalytic reaction in the secondary reactor 8, the obtained liquid sulfur is collected, and the condensed Claus tail gas continuously enters a subsequent reaction;
a tail gas heater 10, wherein the separated Claus tail gas enters the tail gas heater 10 for heating treatment;
a hydrogenation reactor 11, wherein the hydrogenation reactor 11 is fully filled with a high-activity hydrogenation catalyst, and the Claus tail gas after heating is used for hydrogenation conversion of sulfur-containing compounds into H in the hydrogenation reactor 11 2 S, can ensure H removal in the Claus tail gas 2 Fully hydrogenating or hydrolyzing sulfur-containing compounds except S to obtain H-containing compounds 2 S, hydrogenation tail gas; controlling the inlet temperature of the hydrogenation reactor to be 200-250 ℃, preferably 200-230 ℃;
quench tower 13, said H-containing 2 S, enabling hydrogenated tail gas to enter the quenching tower 13 for cooling treatment; in the reaction process, the pH value change of the quenching tower 13 is required to be observed at any time, the pH value of the quenching tower 13 is controlled to be 7-10, and ammonia injection or alkali injection measures are adopted if necessary;
an absorption tower 14, wherein an amine liquid is arranged in the absorption tower 14 and is used for absorbing H in the hydrogenation tail gas 2 S, 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;
the incinerator 16 incinerates the tail gas purified by the absorber 14 and discharges the tail gas through the chimney 17.
The method for starting the sulfur recovery process shown in fig. 1 specifically comprises the following steps:
(1) During the opening process, the acid gas generated by the upstream device is directly introduced 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 in a natural gas combustion mode, the heating rate is 10-25 ℃/H, and when the H in the amine liquid of the absorption tower 14 is detected 2 When the S concentration reaches 5-8g/l, an amine liquid circulating regeneration system is established, the top temperature of the regeneration tower 15 is controlled to be 110-115 ℃, the temperature of the tower bottom is controlled to be 115-120 ℃, and the regenerated acid gas enters an acid gas buffer tank 18 for temporary storage;
(2) When the pressure of the acid gas buffer tank 18 is detected to reach 20-40Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into the sulfur making furnace 1, air distribution is carried out according to the complete combustion of the liquid sulfur, and the liquid sulfur is completely combusted in the sulfur making furnace 1 to generate SO 2 SO after combustion 2 Mixing the regenerated acid gas with the regenerated acid gas from the regeneration tower 15 at any position in the rear part of the sulfur making 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 sequentially entering a subsequent reaction unit for sulfur recovery after mixing;
when the acid gas load reaches 10-25%, the acid gas amount introduced into the absorption tower can be gradually reduced (namely, the line 1 is gradually closed) until the line 1 is gradually cut off, meanwhile, the acid gas is slowly introduced into the sulfur producing furnace 1 (namely, the line 2 is gradually opened), and the air quantity is adjusted according to the furnace chamber temperature, the reactor temperature and the like of the sulfur producing furnace by an online instrument, so that the startup of a sulfur recovery device is completed, and normal production is shifted;
(3) The separated reaction furnace tail gas is heated by the primary heater 4 and then enters the primary reactor 5, claus reaction is carried out under the action of a catalyst with selected grading, the reacted catalytic tail gas enters the secondary condenser 6 for condensation, elemental sulfur is collected, the condensed catalytic tail gas is heated by the secondary heater 7 and then continuously enters the secondary reactor 8 for reaction, and the elemental sulfur and the Claus tail gas are generated after Claus catalytic conversion under the action of the catalyst; the elemental sulfur and the Claus tail gas enter the three-stage condenser 9 for condensation, the liquid sulfur generated after the condensation is also collected, and the Claus tail gas after the condensation (containing trace elements of sulfur and H 2 S、SO 2 And COS, CS 2 The sulfur compounds) are heated by a tail gas heater 10 and then enter a hydrogenation reactor 11 to carry elemental sulfur and SO in the tail gas under the action of a hydrogenation catalyst 2 All hydrogenation is converted into H 2 S，COS、CS 2 Hydrolysis to H 2 S, S; 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 the amine liquid absorbs H in hydrogenation tail gas 2 S, S; the rest of the purified tail gas is led into the incinerator 16 to be discharged through the chimney 17 after being incinerated, so that the new environmental protection standard requirement is met.
Example 1
The sulfur device is started up at a certain 15 ten thousand tons/year, and the starting method is as follows: the upstream device generates acid gas and then directly introduces the acid gas into the absorption tower 14, namely, the line 1 is opened, the line 2 is closed, the temperature of the top of the absorption tower 14 is controlled to 35 ℃, the incinerator 16 is ignited, the incinerator adopts a natural gas combustion mode to heat up, the heating rate is 15 ℃/H, and when the H in the amine liquid of the absorption tower 14 is detected 2 When the S concentration reaches 6g/L, an amine liquid circulating regeneration system is established, the top temperature of the regeneration tower 15 is controlled to be 112 ℃, the temperature of the tower kettle is controlled to be 117 ℃, and the regenerated acid gas enters an acid gas buffer tank 18; when the pressure of the buffer tank reaches 20Kpa, the buffer tank is startedThe dynamic liquid sulfur injector takes inert gas as power to carry liquid sulfur into the sulfur producing furnace 1, and the liquid sulfur is completely combusted and distributed according to the liquid sulfur, SO that the liquid sulfur is completely combusted in the sulfur producing furnace to generate SO 2 SO after combustion 2 The regenerated acid gas from the regeneration tower is mixed with any position in the rear part of the sulfur making 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 the mixed acid gas is sequentially fed into a sulfur making unit and a tail gas treatment unit.
The subsequent sulfur producing unit and the tail gas treatment unit are treated according to the existing traditional process, namely, a sulfur producing furnace 1, a waste heat boiler 2, a primary condenser 3, a primary heater 4, a primary reactor 5, a secondary condenser 6, a secondary heater 7, a secondary reactor 8, a tertiary condenser 9, a tail gas heater 10, a hydrogenation reactor 11, a steam generator 12, a quenching tower 13, an absorption tower 14 and an incinerator 16 are sequentially connected.
In the reaction process, the pH value change in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 8, the hearth temperature of the sulfur making furnace 1 is controlled at 1250 ℃, the inlet temperature of the primary reactor 5 is 220 ℃, the inlet temperature of the secondary reactor 8 is 210 ℃, the inlet temperature of the hydrogenation reactor 11 is 220 ℃, and the top temperature of the absorption tower 14 is controlled at 35 ℃.
When the acid gas load reaches 10%, the acid gas quantity of the acid gas introducing absorption tower is gradually reduced (the line 1 is gradually closed) and the quantity of the liquid sulfur introduced into the sulfur producing furnace 1 is gradually reduced until the line 1 is cut off, meanwhile, the acid gas is slowly introduced into the sulfur producing furnace (the line 2 is opened), the air quantity is adjusted according to the furnace chamber temperature, the reactor temperature and the like of the sulfur producing furnace by an online instrument, the startup of the sulfur recovery device is completed, and normal production is shifted.
In the above embodiments of the present invention:
the oxygen-removing catalyst is preferably LS-971 catalyst developed by the institute of petrochemical Oldham company. LS-971 catalyst is a high Claus activity and de-O-leak 2 The protecting type double-function sulfur recovery catalyst is suitable for Claus sulfur recovery device in petrochemical industry, coal chemical industry and other fields, and can be used for the complete bed layer of the Claus reactor of any stage of the sulfur recovery device or layered filling with other catalysts with different functions or types, and a large amount of oxygen leakage can be generated in the process of removing oxygen leakageThe reaction heat is improved, 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 condition, the total sulfur conversion rate can be improved by about 1 to 1.7 percent, and is especially suitable for acid gas H 2 The sulfur recovery device with larger 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 350m 2 Preferably LS-02 catalyst developed by the institute of Mitsubishi Oldham corporation. The LS-02 catalyst is a novel alumina-based sulfur-making catalyst with larger specific surface area and higher pore volume, which is developed on the basis of LS-300, and has high catalytic Claus 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; the catalyst has more reasonable pore structure and more macropores, and the pore structure is in bimodal distribution, so that sulfur generated by the reaction rapidly leaves the pore canal of the catalyst, and the Claus activity and the organic sulfur hydrolysis 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 institute of Oldham's GmbH, the inlet temperature of the hydrogenation reactor can be controlled to 220-260 ℃, the activity of the catalyst is improved by more than 30% compared with that of a common catalyst, the catalyst has excellent low-temperature hydrogenation and hydrolysis activities, and the content of organic sulfur in hydrogenated tail gas can be ensured to be lower than 20ppm.
The catalyst of the invention can be purchased from market, and the physicochemical properties and technical indexes are shown in the following table 1.
TABLE 1 catalyst physicochemical Properties and technical indicators
| Physical and chemical Properties | LS-971 | LS-02 | LSH-03A |
| Appearance of | Reddish brown spherical shape | White spherical shape | Grey green clover strip |
| Specification/mm | Φ3～Φ5 | Φ4～6 | Φ3×5-10 |
| intensity/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/m 2 ·g -1 | ≥220 | ≥350 | ≥180 |
| Pore volume/mL.g -1 | ≥0.35 | ≥0.45 | ≥0.35 |
| Main component | Al 2 O 3 +Fe 2 O 3 | Al 2 O 3 | CoO+MoO 3 +Al 2 O 3 |
Comparative example 1
The sulfur recovery process of this comparative example is different from the process of example 1 only in that the step of directly introducing the acid gas into the absorption column for treatment at the time of the start-up is omitted according to the conventional claus+scot process, and the acid gas produced by the upstream apparatus is directly introduced into the sulfur producing furnace 1 for treatment in the conventional manner.
Compared with the traditional Claus+SCOT process in comparative example 1, the process in the embodiment 1 of the invention solves the problems of directly discharging acid gas into a torch and the like in the starting process, and the flue gas SO is generated during the starting and running processes of the process 2 Are all smaller than 80mg/m 3 Meets the latest environmental protection requirement.
Example 2
The sulfur device is started up in 8 ten thousand tons/year, and the starting method is as follows: the upstream device generates acid gas and then directly introduces the acid gas into the absorption tower, the stage is that the line 1 is opened, the line 2 is closed, the temperature of the tower top of the absorption tower is controlled to 25 ℃, the incinerator is ignited, the incinerator is heated in a natural gas combustion mode, the heating rate is 10 ℃/H, and when the H in the amine liquid of the absorption tower is detected 2 When the S concentration reaches 8g/L, an amine liquid circulating regeneration system is established, the temperature of the top of the regeneration tower is controlled to be 115 ℃, the temperature of the tower bottom is controlled to be 120 ℃, and the regenerated acid gas enters an acid gas buffer tank; when the pressure of the buffer tank reaches 40Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into a sulfur making furnace, and air distribution is carried out according to complete combustion of the liquid sulfur, so that the liquid sulfur is in the sulfur making furnaceInternal combustion to form SO 2 SO after combustion 2 Mixing the regenerated acid gas with any position in the rear part of the sulfur making furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and sequentially feeding the mixed acid gas into a sulfur making unit and a tail gas treatment unit.
In the reaction process, the pH value change in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 7, the hearth temperature 1180 ℃ of the sulfur producing furnace 1 is controlled, the inlet temperature of the primary reactor 5 is 240 ℃, the inlet temperature of the secondary reactor 8 is 220 ℃, the inlet temperature of the hydrogenation reactor 11 is 230 ℃, and the top temperature of the absorption tower 14 is controlled at 25 ℃.
When the acid gas load reaches 25%, the acid gas quantity of the acid gas introducing absorption tower is gradually reduced (the line 1 is gradually closed) and the liquid sulfur is introduced into the sulfur producing furnace until the line 1 is cut off, meanwhile, the acid gas is slowly introduced into the sulfur producing furnace (the line 2 is opened), and the air quantity is adjusted according to the furnace chamber temperature of the sulfur producing furnace, the temperature of a reactor and the like of an online instrument, so that the startup of a sulfur recovery device is completed, and normal production is shifted.
Comparative example 2
The sulfur recovery process of this comparative example is different from the process of example 2 only in that the step of directly introducing the acid gas into the absorption column for treatment at the time of start-up is omitted according to the conventional claus+scot process, and the acid gas produced by the upstream apparatus is directly introduced into the sulfur producing furnace 1 for treatment in the conventional manner.
Compared with the traditional Claus+SCOT process in comparative example 2, the process in example 2 solves the problems of directly discharging acid gas into a torch in the starting process, and adopts the process to start and operate flue gas SO 2 Are all smaller than 60mg/m 3 Meets the latest environmental protection requirement.
Example 3
The sulfur device is started up in 10 ten thousand tons/year, and the starting method is as follows: the upstream device generates acid gas and then directly introduces the acid gas into an absorption tower, namely, a line 1 is opened, a line 2 is closed, the temperature of the tower top of the absorption tower is controlled to be 30 ℃, an incinerator is ignited, the incinerator is heated in a natural gas combustion mode, the heating rate is 25 ℃/H, and when H in the amine liquid of the absorption tower is detected 2 When the S concentration reaches 5g/L, build upThe amine liquid circulating and regenerating system controls the temperature of the top of the regenerating tower to 110 ℃ and the temperature of the bottom of the tower to 115 ℃, and the regenerated acid gas enters 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 a sulfur producing furnace, and air distribution is carried out according to the complete combustion of the liquid sulfur, SO that the liquid sulfur is completely combusted in the sulfur producing furnace to generate SO 2 SO after combustion 2 Mixing the regenerated acid gas with any position in the rear part of the sulfur making furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and sequentially feeding the mixed acid gas into a sulfur making unit and a tail gas treatment unit.
In the reaction process, the pH value change in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 9, the hearth temperature of the sulfur making furnace 1 is controlled at 1310 ℃, the inlet temperature of the primary reactor 5 is 230 ℃, the inlet temperature of the secondary reactor 8 is 212 ℃, the inlet temperature of the hydrogenation reactor 11 is 233 ℃, and the top temperature of the absorption tower 14 is controlled at 30 ℃.
When the acid gas load reaches 15%, gradually reducing the acid gas quantity of the acid gas leading absorption tower (gradually closing the circuit 1) and the quantity of the liquid sulfur to the sulfur producing furnace until the circuit 1 is cut off, and slowly leading the acid gas to the sulfur producing furnace (opening the circuit 2), adjusting the air quantity according to the furnace chamber temperature of the sulfur producing furnace, the temperature of a reactor and the like of an online instrument, completing the startup of a sulfur recovery device, and turning into normal production.
Comparative example 3
The sulfur recovery process of this comparative example is different from the process of example 3 only in that the step of directly introducing the acid gas into the absorption column for treatment at the time of the start-up is omitted according to the conventional claus+scot process, and the acid gas produced by the upstream apparatus is directly introduced into the sulfur producing furnace 1 for treatment in the conventional manner.
Compared with the traditional Claus+SCOT process in comparative example 3, the process in example 3 solves the problems of directly discharging acid gas into a torch in the starting process, and adopts the process to start and operate flue gas SO 2 Are all less than 70mg/m 3 Meets the latest environmental protection requirement.
Example 4
Some 4 ten thousand tons/year sulfur device starts working, and the starting method is as followsThe following steps: the upstream device generates acid gas and then directly introduces the acid gas into an absorption tower, namely, a line 1 is opened, a line 2 is closed, the temperature of the tower top of the absorption tower is controlled to be 32 ℃, an incinerator is ignited, the incinerator is heated in a natural gas combustion mode, the heating rate is 12 ℃/H, and when the H in the amine liquid of the absorption tower is detected 2 When the S concentration reaches 7g/L, an amine liquid circulating regeneration system is established, the temperature of the top of the regeneration tower is controlled to be 113 ℃, the temperature of the tower kettle is controlled to be 117 ℃, the regenerated acid gas enters an acid gas buffer tank, when the pressure of the buffer tank reaches 26Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into a sulfur making furnace, and air distribution is carried out according to the complete combustion of the liquid sulfur, SO that the liquid sulfur is completely combusted in the sulfur making furnace to generate SO 2 SO after combustion 2 Mixing the regenerated acid gas with any position in the rear part of the sulfur making furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and sequentially feeding the mixed acid gas into a sulfur making unit and a tail gas treatment unit.
In the reaction process, the pH value change in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 8, and ammonia injection or alkali injection measures are adopted if necessary; and the hearth temperature of the sulfur producing furnace 1 is controlled to 1225 ℃, the inlet temperature of the primary reactor 5 is 228 ℃, the inlet temperature of the secondary reactor 8 is 218 ℃, the inlet temperature of the hydrogenation reactor 11 is 235 ℃, and the top temperature of the absorption tower 14 is controlled to 32 ℃.
When the acid gas load reaches 13%, gradually reducing the acid gas quantity of an acid gas leading absorption tower (gradually closing a circuit 1) and the quantity of liquid sulfur to a sulfur making furnace until the circuit 1 is cut off, and slowly leading the acid gas to the sulfur making furnace (opening the circuit 2), adjusting the air quantity according to the furnace chamber temperature of the sulfur making furnace, the temperature of a reactor and the like of an online instrument, completing the startup of a sulfur recovery device, and turning into normal production.
Comparative example 4
The sulfur recovery process of this comparative example is different from the process of example 4 only in that the step of directly introducing the acid gas into the absorption column for treatment at the time of the start-up is omitted according to the conventional claus+scot process, and the acid gas produced by the upstream apparatus is directly introduced into the sulfur producing furnace 1 for treatment in the conventional manner.
The procedure in example 4 of the present invention is compared to conventional C in comparative example 4laus+SCOT technology solves the problems of directly discharging acid gas into a torch in the starting process, and the like, and flue gas SO is generated during the starting and running processes of the technology 2 Are all smaller than 55mg/m 3 Meets the latest environmental protection requirement.
Example 5
The sulfur device is started up for 7 ten thousand tons/year, and the starting method is as follows: 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 tower top of the absorption tower is controlled to be 28 ℃, the incinerator is ignited, the incinerator is heated in a natural gas combustion mode, the heating rate is 16 ℃/H, and when the H in the amine liquid of the absorption tower is detected 2 When the S concentration reaches 5g/l, an amine liquid circulating regeneration system is established, the temperature of the top of the regeneration tower is controlled to be 114 ℃, the temperature of the tower kettle is controlled to be 118 ℃, the regenerated acid gas enters an acid gas buffer tank, when the pressure of the buffer tank reaches 31Kpa, a liquid sulfur injector is started, inert gas is used as power to carry liquid sulfur into a sulfur making furnace, and air distribution is carried out according to the complete combustion of the liquid sulfur, SO that the liquid sulfur is completely combusted in the sulfur making furnace to generate SO 2 SO after combustion 2 Mixing the regenerated acid gas with any position in the rear part of the sulfur making furnace, the rear part of the waste heat boiler, the inlet of the primary heater and the inlet of the primary reactor, and sequentially feeding the mixed acid gas into a sulfur making unit and a tail gas treatment unit.
In the reaction process, the pH value change in the quenching tower 13 is observed at any time, the pH value in the quenching tower 13 is controlled at 9, and ammonia injection or alkali injection measures are adopted if necessary; and the furnace temperature 1160 ℃ of the sulfur producing furnace 1 is controlled, the inlet temperature 225 ℃ of the primary reactor 5, the inlet temperature 221 ℃ of the secondary reactor 8, the inlet temperature 235 ℃ of the hydrogenation reactor 11 and the top temperature of the absorption tower 14 are controlled to be 28 ℃.
When the acid gas load reaches 12%, gradually reducing the acid gas quantity of an acid gas introducing absorption tower (gradually closing a circuit 1) and the quantity of liquid sulfur to a sulfur making furnace until the circuit 1 is cut off, and slowly introducing the acid gas to the sulfur making furnace (opening the circuit 2), adjusting the air quantity according to the furnace chamber temperature of the sulfur making furnace, the temperature of a reactor and the like of an online instrument, completing the startup of a sulfur recovery device, and turning into normal production.
Comparative example 5
The sulfur recovery process of this comparative example differs from the process of example 5 only in that the step of directly introducing the acid gas into the absorber for treatment at the time of start-up is omitted in accordance with the conventional claus+scot process, and the acid gas produced by the upstream apparatus is directly introduced into the sulfur producing furnace 1 for treatment in accordance with the conventional manner.
Compared with the traditional Claus+SCOT process in comparative example 5, the process in example 5 solves the problems of directly discharging acid gas into a torch in the starting process, and adopts the process to start and operate flue gas SO 2 Are all smaller than 90mg/m 3 Meets the latest environmental protection requirement.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The method for starting the sulfur recovery process is characterized by comprising the following steps of:
(1) In the initial stage of starting operation, the acid gas produced by the upstream device is directly introduced into an absorption tower for enrichment absorption, and when H in the absorption tower is detected 2 When the S concentration reaches a preset value, starting a regeneration tower to perform amine liquid circulation regeneration treatment, and collecting the regenerated acid gas for later use;
(2) The liquid sulfur to be treated is input into a sulfur producing furnace, and is completely combusted according to the liquid sulfur to be distributed with air, SO that the liquid sulfur is completely combusted in the sulfur producing furnace to generate SO 2 ；
(3) SO after combustion 2 Mixing the regenerated acid gas with any position between the rear part of the sulfur producing furnace and the inlet of the Claus reactor, performing Claus reaction, and condensing and recovering the obtained liquid sulfur; carrying out hydrogenation treatment on the generated Claus tail gas to carry out tail gas treatment;
in the step (2), when the acid gas is stable and the system load meets the requirement, gradually reducing the gas quantity of the acid gas introduced into the absorption tower, slowly introducing the acid gas generated by an upstream device into the sulfur-making furnace until the sulfur recovery device is started, and turning into normal production.
2. The method for starting up the sulfur recovery process according to claim 1, wherein the step (1) further comprises a step of starting up an incinerator to perform acid gas regeneration tail gas treatment, and the temperature rising rate of the incinerator is controlled to be 10-25 ℃/h.
3. The method according to claim 1 or 2, wherein in the step (1), H in the amine liquid of the absorption tower is controlled 2 And when S reaches 5-8g/L, starting the regeneration tower.
4. The method according to claim 1 or 2, wherein in the step (1), the temperature of the absorption tower is controlled to be 20-40 ℃, the temperature of the top of the regeneration tower is controlled to be 110-115 ℃, and the temperature of the bottom of the tower is controlled to be 115-120 ℃.
5. The method according to claim 1 or 2, wherein in the step (2), inert gas is used as power to carry the liquid sulfur into the sulfur producing furnace, and the temperature of the inert gas is controlled to be 120-140 ℃.
6. The method of starting up a sulfur recovery process according to claim 1 or 2, wherein in step (3);
the catalyst of the claus reaction treatment step comprises a claus catalyst;
the temperature of the claus reaction step is 200-250 ℃.
7. The method according to claim 1 or 2, wherein in the step (3):
the catalyst of the hydrogenation treatment step comprises a pre-sulfided claus tail gas hydrogenation catalyst, an oxidized claus tail gas hydrogenation catalyst or a sulfided oxidized claus tail gas hydrogenation catalyst;
the temperature of the hydrogenation reaction step is 200-250 ℃.
8. The method according to claim 1 or 2, wherein in the step (3), the tail gas treatment step includes a step of introducing tail gas into the absorption tower and a step of introducing the tail gas into the regeneration tower for regeneration.
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