CN112299378B - Sulfur recovery device filled with sulfurized hydrogenation catalyst and start-up method - Google Patents
Sulfur recovery device filled with sulfurized hydrogenation catalyst and start-up method Download PDFInfo
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- CN112299378B CN112299378B CN201910711796.4A CN201910711796A CN112299378B CN 112299378 B CN112299378 B CN 112299378B CN 201910711796 A CN201910711796 A CN 201910711796A CN 112299378 B CN112299378 B CN 112299378B
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- C01B17/00—Sulfur; Compounds thereof
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Abstract
The invention belongs to the technical field of sulfur recovery, and particularly relates to a sulfur recovery device filled with a vulcanized hydrogenation catalyst and a start-up method. The device comprises a main line, a first jumper, a second jumper, a third jumper, a delivery pump, a valve and an instrument device for automatic control, wherein the delivery pump, the valve and the instrument device are arranged on the pipeline. The invention also provides a startup method of the sulfur recovery device based on the filling of the sulfuration state hydrogenation catalyst, which comprises the steps of establishing a large flow during startup, isolating the hydrogenation reactor and reasonably utilizing the quench tower, communicating the absorption tower after determining an oxygen deficiency condition, and directly walking the normal flow of the sulfur recovery device, namely, the main line is in an open state, and the first crossover line, the second crossover line and the third crossover line are in a closed state, so that the green startup of the sulfur device is realized. The method adopts natural gas and air for combustion, air distribution is easy to control, catalyst temperature runaway in the process of start-up can be effectively avoided, and convenience is provided for standard emission of tail gas.
Description
Technical Field
The invention belongs to the technical field of sulfur recovery, relates to sulfur recovery in petroleum refining, coal chemical industry and natural gas purification industry, and particularly relates to a sulfur recovery device filled with a vulcanized hydrogenation catalyst and a start-up method.
Background
The emission standard GB31570-2015 of the industrial pollutants for refining petroleum specifies that the emission concentration limit value of the atmospheric pollutants of the sulfur recovery device is less than 400mg/Nm3Especially less than 100mg/Nm3. The regulation does not set the flue gas SO during the startup and shutdown of the sulfur recovery device2The emission concentration is regulated, so that the requirement of 'emission standard GB31570-2015 for petroleum refining industry pollutants' is met during start-up and shut-down periods, and the sulfur recovery device is tested greatly during start-up and shut-down periods.
The sulfur recovery device is divided into a sulfur production unit and a tail gas treatment unit. The sulfur production unit and the tail gas treatment unit are relatively independent during the starting. The conventional starting method of the sulfur production unit is that gas and air are used for combustion to raise the temperature, and the gas combustion gas is directly burned by an incinerator and then discharged by a chimney after passing through a reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor and a tertiary condenser. Because the gas components are complex, the air distribution is not easy to control, the catalyst is easy to be inactivated by carbon deposition, the catalyst is easy to fly when the sulfur production unit and the tail gas treatment unit are communicated, and inevitable impurities such as sulfur and the like exist in the pipeline of the sulfur recovery device, sulfur reacts with oxygen to generate SO in the start-up stage2The emission will exceed the standard. The exhaust gas treatment unit is filled with two catalysts: one is an oxidation state catalyst and the other is a sulfided state catalyst. The sulfuration state catalyst avoids the startup sulfuration process and can effectively reduce SO2And (5) discharging.
Chinese patent CN105084322A discloses reduction of SO in hydrogenation reduction catalyst during hydrogenation presulfiding2Process for discharging concentrations in two steps, the first step being to contain H2Introducing the acidic gas of S into a hydrogenation reduction reactor, and adding H under the condition of hydrogenation presulfiding2S is contacted with a hydrogenation reduction catalyst to carry out hydrogenation pre-vulcanization reaction to obtain hydrogenation pre-vulcanizationVulcanizing the tail gas; wherein, the hydrogenation pre-sulfuration condition leads the sulfur in the hydrogenation pre-sulfuration tail gas to be totally expressed as H2The form of S exists; secondly, cooling the hydrogenation pre-vulcanization tail gas, and then contacting the cooled hydrogenation pre-vulcanization tail gas with absorption liquid containing amine liquid to obtain residual gas and absorbed H2And residual gas of the absorption liquid containing the amine liquid of the S is discharged after being incinerated. The method can only meet the emission of 960mg/m in the start-up process3And the method can not ensure that the whole start-up process meets 960mg/m3The catalyst temperature runaway phenomenon is easily caused during the start-up period.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a sulfur recovery device filled with a vulcanized hydrogenation catalyst and a start-up method, wherein a reaction furnace is combusted by adopting natural gas and air, a large flow is established during start-up, a hydrogenation reactor is isolated, a quenching tower is reasonably utilized, and the pH value of the quenching tower is controlled to be 7-10. Ensures that the sulfur recovery device reaches the standard and discharges during the start-up period, has low construction and operation cost, saves the energy consumption of the device and SO2The emission reduction is obvious, and the catalyst is not easy to generate temperature runaway phenomenon in the start-up process.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
the invention provides a sulfur recovery device filled with a sulfurized hydrogenation catalyst, which comprises a main line, a first crossover line, a second crossover line, a third crossover line, a delivery pump, a valve and an instrument device for automatic control, wherein the delivery pump, the valve and the instrument device are arranged on the pipeline;
the main line comprises a reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor, a tertiary condenser, a tail gas heater, a hydrogenation reactor, a steam generator, a quench tower, an absorption tower, an incinerator and a chimney which are sequentially communicated, wherein an air inlet of the reaction furnace is connected with an air inlet and a natural gas inlet;
the air inlet of the first overline is arranged on a connecting pipeline between the three-stage condenser and the tail gas heater, and the air outlet of the first overline is arranged on a connecting pipeline between the absorption tower and the incinerator;
the gas inlet of the second overline is arranged on a connecting pipeline between the quenching tower and the absorption tower, and the gas outlet of the second overline is arranged on a connecting pipeline between the absorption tower and the incinerator;
and the air inlet of the third overline is arranged on a connecting pipeline between the three-stage condenser and the tail gas heater, and the air outlet of the third overline is arranged on a connecting pipeline between the steam generator and the quench tower.
Further, a rich liquid outlet at the lower part of the absorption tower is communicated with the upper part of the regeneration tower through a rich solvent pump, and a lean liquid outlet at the lower part of the regeneration tower is connected with an absorbent inlet at the upper part of the absorption tower.
The invention also provides a start-up method of the sulfur recovery device based on the filling of the sulfuration state hydrogenation catalyst, which comprises the following steps:
(1) introducing natural gas and air into the reaction furnace in proportion and burning, adjusting a tube pass valve to enable natural gas burning tail gas to be discharged from the three-stage condenser and then directly enter the quenching tower through a third span line, and then directly enter the incinerator for incineration through a second span line after being discharged from the top of the quenching tower;
(2) when there is no liquid sulfur in the tube pass at the outlet of the three-stage condenser, and/or SO2When the content is less than the set value, the ratio of the introduced natural gas to the introduced air is adjusted to ensure that the natural gas and the air are oxygen-deficient to burn;
(3) when the tube pass of the outlet of the three-stage condenser is O2Content, SO2When the content is less than the set value, adjusting a tube pass valve to enable the natural gas combustion tail gas to directly enter the incinerator for incineration from the outlet of the three-stage condenser through a first cross line;
(4) after the natural gas combustion tail gas directly enters the incinerator for incineration from the outlet of the three-stage condenser through the first crossover line, the tube side valve is adjusted, and the first crossover line, the second crossover line and the circulating line pipeline are closed, so that the natural gas combustion tail gas enters the incinerator for combustion through the main line;
(5) after the natural gas combustion tail gas enters the incinerator for combustion through the main line, the acid gas is slowly introduced into the reaction furnace, meanwhile, the consumption of the natural gas is reduced, the air quantity is adjusted, and the start-up of the sulfur recovery device is realized.
Specifically, before natural gas is introduced in the step (1), the temperature of the reaction furnace and the incinerator is raised in a natural gas combustion mode, and the temperature raising rate is 10-25 ℃/h; and (3) maintaining the waste heat boiler, the first-stage condenser, the second-stage condenser and the third-stage condenser at 120-150 ℃, and maintaining the pH value of the quenching water in the quenching tower at 7-10 in the step (1).
Specifically, in the step (1), the temperature of a hearth of the reaction furnace is 900-1400 ℃, the inlet temperature of the primary reactor is 200-250 ℃, the inlet temperature of the secondary reactor is 200-250 ℃, the inlet temperature of the hydrogenation reactor is 200-250 ℃, and the temperature of the top of the absorption tower is 20-38 ℃.
Preferably, in the step (1), the temperature of a hearth of the reaction furnace is 1000-1300 ℃, the temperature of an inlet of the primary reactor is 220-240 ℃, the temperature of an inlet of the secondary reactor is 210-230 ℃, the temperature of an inlet of the hydrogenation reactor is 200-230 ℃, and the temperature of the top of the absorption tower is 25-35 ℃.
Specifically, the natural gas and air in the step (1) are mixed according to the ratio of 1: introducing the mixture into a reaction furnace in a ratio of 1-1.5, and carrying out oxygen-deficient combustion on the natural gas and the air in the step (2) according to a ratio of 1: 8.5-9.
Specifically, SO in the step (2)2The content is 80-100mg/m3When in use, natural gas and air are burnt under oxygen.
Specifically, O in the step (3) and the step (5)2The content setting value is 0.2% v/v, SO2The content setting value is 100mg/m3。
Specifically, before the acid gas is introduced into the main line in the step (5), an amine liquid circulating system is established on the absorption tower in a connecting mode.
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.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the invention provides a startup method of a sulfur recovery device filled with a vulcanized hydrogenation catalyst, which adopts natural gas and air for combustion, is easy to control air distribution, and can effectively avoid catalyst temperature runaway in the startup process and provide convenient conditions for tail gas emission reaching the standard.
(2) The method comprises the steps of establishing a large flow during starting, reasonably utilizing a quench tower, communicating a hydrogenation reactor and an absorption tower after determining an oxygen deficiency condition, and directly walking the normal flow of the sulfur recovery device, namely, a main line is in an open state, and a first crossover, a second crossover and a third crossover are in a closed state, so that green starting of the sulfur device is realized.
(3) The invention has the characteristics of low investment and easy control of air distribution, and ensures the flue gas SO in the process of start-up2The discharge is less than 100mg/m3. The method is widely applied to the start-up process of the sulfur device in the industries of petroleum refining, natural gas purification, coal chemical industry and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a flow chart of the start-up method of a sulfur recovery device filled with a sulfided hydrogenation catalyst according to the present invention;
the respective symbols in the figure are as follows: the system comprises a reaction 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 quench tower 13, an absorption tower 14, a regeneration tower 15, an incinerator 16, a chimney 17, a circulating water pump 18, a rich solvent pump 19, a first span line 20, a second span line 21, a third span line 22, an air inlet A, a natural gas inlet B and a sewage outlet C.
Detailed Description
In the description of the present invention, it should be noted that the terms "vertical", "upper", "lower", "horizontal", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
The invention will be further explained with reference to the drawings.
As shown in FIG. 1, the sulfur recovery device filled with hydrogenation catalyst in a sulfurized state provided by the invention comprises a main line, a first crossover line 20, a second crossover line 21 and a third crossover line 22, as well as a delivery pump, a valve and an instrument device for automatic control which are arranged on the connecting pipeline.
The main line comprises a reaction 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 quench tower 13, an absorption tower 14, an incinerator 16 and a chimney 17 which are sequentially communicated, and an air inlet of the reaction furnace is connected with an air inlet A and a natural gas inlet B;
a hydrogenation reactor is filled with a sulfurized hydrogenation catalyst.
The rich liquid outlet at the lower part of the absorption tower is communicated with the upper part of the regeneration tower 15 through a rich solvent pump 19, and the lean liquid outlet at the lower part of the regeneration tower is connected with the absorbent inlet at the upper part of the absorption tower.
The liquid phase outlet at the bottom of the quenching tower is connected with a circulating water pump 18, the quenching liquid discharged by the circulating water pump is discharged into a sewage treatment device through a sewage outlet C, and part of the quenching liquid enters the quenching tower to cool the tail gas through cooling circulation.
The air inlet of the first overline is arranged on a connecting pipeline between the three-stage condenser and the tail gas heater, and the air outlet of the first overline is arranged on a connecting pipeline between the absorption tower and the incinerator.
The air inlet of the second overline is arranged on a connecting pipeline between the quenching tower and the absorption tower, and the air outlet of the second overline is arranged on a connecting pipeline between the absorption tower and the incinerator.
The air inlet of the third overline is arranged on a connecting pipeline between the three-stage condenser and the tail gas heater, and the air outlet of the third overline is arranged on a connecting pipeline between the steam generator and the quench tower.
In order to avoid repetition, the raw materials and preparation condition parameters related to this specific embodiment are described below in a unified manner, and are not described in detail in the specific embodiment:
(1) before introducing natural gas, the reaction furnace and the incinerator are heated in a natural gas combustion mode, and the heating rate is 10-25 ℃/h; the waste heat boiler, the first-stage condenser, the second-stage condenser and the third-stage condenser are maintained at 120-150 ℃, and can be heated by adopting medium-pressure steam, superheated gas and the like, so that the temperature of equipment is ensured to be higher than the dew point corrosion temperature in the start-up process, and the dew point corrosion is prevented. Introducing air and natural gas into a reaction furnace according to the ratio of 10: 1-11: 1, burning, adjusting a tube pass valve to enable natural gas burning tail gas to be discharged from a three-stage condenser, directly enter a quenching tower through a third span line, then be discharged from the top of the quenching tower, and directly enter an incinerator through a second span line for incineration, so as to drive off sulfur in the reaction furnace and a pipeline and avoid CO and H generated by oxygen-deficient combustion2And the sulfur reacts with the sulfur to generate COS, so that the emission exceeds the standard.
The pH value of the quenching tower is observed to change at any moment, the pH value of the quenching water in the quenching tower is controlled to be 7-10, and measures of ammonia injection or alkali injection are taken if necessary. Controlling the temperature of a hearth of the reaction furnace to be between 900 and 1400 ℃, preferably between 1000 and 1300 ℃, the inlet temperature of a primary reactor to be between 200 and 250 ℃, preferably between 220 and 240 ℃, the inlet temperature of a secondary reactor to be between 200 and 250 ℃, preferably between 210 and 230 ℃, the inlet temperature of a hydrogenation reactor to be between 200 and 250 ℃, preferably between 200 and 230 ℃, and the temperature of the top of an absorption tower to be between 20 and 38 ℃, preferably between 25 and 35 ℃. The absorption tower is in a normal operation state in advance, SO that the flue gas SO in the whole operation process is ensured2Always kept at 100mg/m3The following.
(2) Performing a target test at the outlet position of the three-stage condenser, and/or detecting the SO at the outlet of the three-stage condenser by using a portable smoke instrument when no liquid sulfur exists2When the content is 80-100mg/m3And adjusting the ratio of introducing natural gas and air to be 1: 8.5-9, so that the natural gas and the air are subjected to oxygen-deficient combustion.
(3) When the tube pass of the outlet of the three-stage condenser is O2The content is less than the set value of 0.2% v/v, SO2The content is less than the set value of 100mg/m3When the natural gas is burnt, the tube pass valve is adjusted to lead the natural gas burning tail gas to be discharged from the three-stage condenserThe port directly enters an incinerator for incineration through a first cross line.
(4) After the natural gas combustion tail gas directly enters the incinerator for incineration from the outlet of the three-stage condenser through the first cross line, the tube side valve is adjusted, the first cross line, the second cross line and the circulating line pipeline are closed, and the natural gas combustion tail gas enters the incinerator for combustion through the main line. Before the acidic gas is introduced into the reaction furnace, the absorption tower is connected with an amine liquid circulating system.
(5) After the natural gas combustion tail gas enters the incinerator for combustion through the main line, the acid gas is slowly introduced into the reaction furnace, meanwhile, the using amount of the natural gas is reduced, and the air quantity is adjusted according to the detection data of the online detector, the hearth temperature of the reaction furnace, the temperature of the reactor and the like, so that the start-up of the sulfur recovery device is realized.
Example 1
The start-up method of a certain 8 ten thousand ton/year sulfur device is as follows: the reaction furnace is ignited by adopting a mode of peroxy combustion of natural gas and air, the temperature rise rate is 15 ℃/h, and an amine liquid circulating system is established. The temperature of the waste heat boiler and the three condensers is maintained at 130 ℃, a large flow main line is established, and the large flow main line is sequentially connected with a reaction furnace, the waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor, a tertiary condenser, a tail gas heater, a hydrogenation reactor, a steam generator, a quench tower, an absorption tower and an incinerator.
The reaction furnace is heated by adopting air and natural gas according to a combustion mode of 10: 1-11: 1, the heating rate is 20 ℃/h, the reaction furnace sequentially passes through the large flow, and the pH value of the rapid cooling water in the rapid cooling tower is controlled at 9. The furnace temperature of the reaction furnace is 1100 ℃, the inlet temperature of the primary reactor is 240 ℃, the inlet temperature of the secondary reactor is 220 ℃, the inlet temperature of the hydrogenation reactor is 230 ℃, and the temperature of the top of the absorption tower is controlled to be 38 ℃. The combustion tail gas of the natural gas directly enters the incinerator through the second span line and the third span line.
Performing a targeting test at the outlet position of the three-stage condenser, and detecting the SO at the outlet of the three-stage condenser by using a portable smoke instrument when no liquid sulfur exists2When the content is 80-100mg/m3When in use, natural gas and air are changed into oxygen-deficient combustion, and the volume flow ratio of the air to the natural gas is controlled to be 9. By means of portabilityFormula flue gas appearance detects SO2And O2In an amount of O2Volume content less than 0.2%, SO2The content is less than 100mg/m3When the natural gas is used, the natural gas combustion gas enters a first cross-line pipeline after passing through a three-stage condenser or before passing through a tail gas heater and is sent into an incinerator for incineration.
The natural gas combustion gas is communicated with the whole large flow path main line, namely, the tail gas heater, the hydrogenation reactor, the steam generator and the absorption tower are also communicated with the whole flow path, so that the normal communication of the sulfur recovery device is realized. The acid gas is slowly introduced, simultaneously the consumption of natural gas is reduced, the air quantity is adjusted, and the flue gas SO in the start-up process of the sulfur recovery device2The emission is 60mg/m3In the following, compared with the start-up procedure of comparative example 1, the energy consumption of the device is saved by 26% during the whole start-up period, and the SO content is reduced by 26%2And 4, emission reduction is carried out.
Comparative example 1
A certain 8 ten thousand tons/year sulfur device is started, and the traditional start-up method is adopted as follows:
the sulfur production unit adopts gas and air peroxide combustion to raise the temperature, the heating rate is 15 ℃/h, and the gas combustion gas is directly burnt by an incinerator and then discharged by a chimney after passing through a reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor and a tertiary condenser. When the temperature of a hearth of a reaction furnace is 1100 ℃, the inlet temperature of a primary reactor is 240 ℃, the inlet temperature of a secondary reactor is 220 ℃ and the inlet temperature of a hydrogenation reactor is 230 ℃, the sulfur-making unit switches the acid gas to burn, the acid gas burning gas directly passes through the reaction furnace, a waste heat boiler, a primary condenser, a primary heater, the primary reactor, a secondary condenser, a secondary heater, the secondary reactor and a tertiary condenser and then is burnt by an incinerator and then is discharged through a chimney, and the flue gas SO2The concentration is up to 30000mg/m3Wait for H2S-2SO2And when the temperature is-0.3 ℃, directly introducing the Claus tail gas of the sulfur production unit into a tail gas treatment unit to realize start-up. The energy consumption of the device in the whole start-up period of the start-up process is-96 kg standard oil/ton.
Example 2
The start-up method of a certain 5.5 ten thousand tons/year sulfur device is as follows: the reaction furnace is ignited by adopting a mode of peroxy combustion of natural gas and air, the temperature rise rate is 10 ℃/h, and an amine liquid circulating system is established. The waste heat boiler and the condenser are maintained at 120 ℃, a large flow path main line is established, and the large flow path main line is sequentially connected with the reaction furnace, the waste heat boiler, the primary condenser, the primary heater, the primary reactor, the secondary condenser, the secondary heater, the secondary reactor, the tertiary condenser, the tail gas heater, the hydrogenation reactor, the steam generator, the quench tower, the absorption tower and the incinerator.
The reaction furnace is heated by adopting air and natural gas according to a combustion mode of 10: 1-11: 1, the heating rate is 15 ℃/h, the reaction furnace sequentially passes through the large flow, and the pH value of the quenching tower is controlled to be 8. The temperature of a hearth of the reaction furnace is 1200 ℃, the inlet temperature of a primary reactor is 210 ℃, the inlet temperature of a secondary reactor is 200 ℃, the inlet temperature of a hydrogenation reactor is 200 ℃, the temperature of the top of an absorption tower is controlled to be 35 ℃, and the combustion tail gas of the natural gas directly enters the incinerator through a second span line and a third span line. Performing a targeting test at the outlet position of the three-stage condenser, and detecting the SO at the outlet of the three-stage condenser by using a portable smoke instrument when no liquid sulfur exists2When the content is 80-100mg/m3When in use, natural gas and air are changed into oxygen-deficient combustion, and the volume flow ratio of the air to the natural gas is controlled to be 8.5. SO detection by using portable smoke instrument2And O2In an amount of O2Less than 0.2%, SO2The content is less than 100mg/m3When the natural gas is used, the natural gas combustion gas enters a first cross-line pipeline after passing through a three-stage condenser or before passing through a tail gas heater and is sent into an incinerator for incineration.
The natural gas combustion gas is communicated with the main line, namely the absorption tower is also communicated into the whole flow, so that the normal communication of the sulfur recovery device is realized. The acid gas is slowly introduced, simultaneously the consumption of natural gas is reduced, the air quantity is adjusted, and the flue gas SO in the start-up process of the sulfur recovery device2The emission is 80mg/m3As follows, compared with the start-up procedure of comparative example 2, the energy consumption of the device is saved by 26% during the whole start-up period, and the SO2And 2.5 tons of emission reduction is realized.
Comparative example 2
A certain 5.5 ten thousand tons/year sulfur device is started, and the traditional start method is as follows:
the sulfur production unit adopts gas and air peroxide combustion to heat up, the heating rate is 10 ℃/h, and the tileThe combustion gas passes through a reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor and a tertiary condenser, is directly burned by an incinerator and then is discharged through a chimney. When the temperature of a hearth of a reaction furnace is 1200 ℃, the inlet temperature of a primary reactor is 210 ℃, the inlet temperature of a secondary reactor is 200 ℃ and the inlet temperature of a hydrogenation reactor is 200 ℃, the sulfur-making unit switches the acid gas to burn, the acid gas burning gas directly passes through the reaction furnace, a waste heat boiler, a primary condenser, a primary heater, the primary reactor, a secondary condenser, a secondary heater, the secondary reactor and a tertiary condenser and then is burnt by an incinerator and then is discharged through a chimney, and the flue gas SO2The concentration is up to 30000mg/m3Wait for H2S-2SO2And when the temperature is-0.3 ℃, directly introducing the Claus tail gas of the sulfur production unit into a tail gas treatment unit to realize start-up. The energy consumption of the device in the whole start-up period of the start-up process is-90 kg standard oil/ton.
Example 3
The start-up method of a certain 1 ten thousand ton/year sulfur device is as follows: the reaction furnace is ignited by adopting a mode of peroxy combustion of natural gas and air, the heating rate is 18 ℃/h, and an amine liquid circulating system is established. The waste heat boiler and the condenser are maintained at 140 ℃, a large-flow main line is established, and the large-flow main line is sequentially connected with the reaction furnace, the waste heat boiler, the primary condenser, the primary heater, the primary reactor, the secondary condenser, the secondary heater, the secondary reactor, the tertiary condenser, the tail gas heater, the hydrogenation reactor, the steam generator, the quench tower, the absorption tower and the incinerator.
The reaction furnace is heated by adopting air and natural gas according to a combustion mode of 10: 1-11: 1, the heating rate is 15 ℃/h, the reaction furnace sequentially passes through the large flow, and the pH value of the quenching tower is controlled at 10. The temperature of a hearth of the reaction furnace is 980 ℃, the inlet temperature of the primary reactor is 230 ℃, the inlet temperature of the secondary reactor is 200 ℃, the inlet temperature of the hydrogenation reactor is 220 ℃, the temperature of the top of the absorption tower is controlled to be 25 ℃, and the combustion tail gas of the natural gas directly enters the incinerator through a second span line and a third span line. Performing a targeting test at the outlet position of the three-stage condenser, and detecting the SO at the outlet of the three-stage condenser by using a portable smoke instrument when no liquid sulfur exists2When the content is 80-100mg/m3Change from time to timeFor the oxygen-deficient combustion of natural gas and air, the volume flow ratio of air and natural gas is controlled to be 8.6. SO detection by using portable smoke instrument2And O2In an amount of O2Less than 0.2%, SO2The content is less than 100mg/m3When the natural gas is used, the natural gas combustion gas enters a first cross-line pipeline after passing through a three-stage condenser or before passing through a tail gas heater and is sent into an incinerator for incineration.
The natural gas combustion gas is communicated with the whole flow, namely the absorption tower is also communicated with the whole flow, so that the normal communication of the sulfur recovery device is realized. The acid gas is slowly introduced, simultaneously the consumption of natural gas is reduced, the air quantity is adjusted, and the flue gas SO in the start-up process of the sulfur recovery device2The emission is 80mg/m3In comparison with the start-up procedure of comparative example 3, the energy consumption of the device is saved by 20% during the whole start-up period, and SO is saved2And 1 ton of emission reduction.
Comparative example 3
A certain 1 ten thousand tons/year sulfur device is started, and the traditional start-up method is adopted as follows:
the sulfur production unit adopts gas and air peroxide combustion to raise the temperature, the heating rate is 18 ℃/h, and the gas combustion gas is directly burnt by the incinerator and then discharged by the chimney after passing through the reaction furnace, the waste heat boiler, the primary condenser, the primary heater, the primary reactor, the secondary condenser, the secondary heater, the secondary reactor and the tertiary condenser. When the temperature of a hearth of a reaction furnace is 980 ℃, the inlet temperature of a primary reactor is 230 ℃, the inlet temperature of a secondary reactor is 200 ℃ and the inlet temperature of a hydrogenation reactor is 220 ℃, the sulfur-making unit switches the acid gas to burn, the acid gas burning gas directly passes through the reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor and a tertiary condenser and then is burnt by an incinerator and then is discharged through a chimney, and the flue gas SO2The concentration is up to 30000mg/m3Wait for H2S-2SO2And when the temperature is-0.3 ℃, directly introducing the Claus tail gas of the sulfur production unit into a tail gas treatment unit to realize start-up. The energy consumption of the device in the whole start-up period of the start-up process is-78 kg standard oil/ton.
Example 4
The start-up method of a certain 4 ten thousand ton/year sulfur device is as follows: the reaction furnace is ignited by adopting a mode of peroxy combustion of natural gas and air, the temperature rise rate is 20 ℃/h, and an amine liquid circulating system is established. The waste heat boiler and the condenser are maintained at 145 ℃, a large flow path is established, and the large flow path is sequentially connected with the reaction furnace, the waste heat boiler, the primary condenser, the primary heater, the primary reactor, the secondary condenser, the secondary heater, the secondary reactor, the tertiary condenser, the tail gas heater, the hydrogenation reactor, the steam generator, the quench tower, the absorption tower and the incinerator.
The reaction furnace is heated by adopting air and natural gas according to a combustion mode of 10: 1-11: 1, the heating rate is 10-25 ℃/h, the reaction furnace sequentially passes through the large flow, and the pH value of the quenching tower is controlled to be 7-10. The temperature of a hearth of the reaction furnace is 1000 ℃, the inlet temperature of the primary reactor is 225 ℃, the inlet temperature of the secondary reactor is 215 ℃, the inlet temperature of the hydrogenation reactor is 220 ℃, the temperature of the top of the absorption tower is controlled to be 30 ℃, and the combustion tail gas of the natural gas directly enters the incinerator through a second span line and a third span line. Performing a targeting test at the outlet position of the three-stage condenser, and detecting the SO at the outlet of the three-stage condenser by using a portable smoke instrument when no liquid sulfur exists2When the content is 80-100mg/m3When in use, natural gas and air are changed into oxygen-deficient combustion, and the volume flow ratio of the air to the natural gas is controlled to be 8.9. SO detection by using portable smoke instrument2And O2In an amount of O2Less than 0.2%, SO2The content is less than 100mg/m3When the natural gas is used, the natural gas combustion gas enters a first cross-line pipeline after passing through a three-stage condenser or before passing through a tail gas heater and is sent into an incinerator for incineration.
The natural gas combustion gas is communicated with the whole flow, namely the absorption tower is also communicated with the whole flow, so that the normal communication of the sulfur recovery device is realized. The acid gas is slowly introduced, simultaneously the consumption of natural gas is reduced, the air quantity is adjusted, and the flue gas SO in the start-up process of the sulfur recovery device2The emission is 80mg/m3In comparison with the start-up step of comparative example 4, the energy consumption of the device is saved by 24 percent and the SO is saved during the whole start-up period2And 2 tons of emission reduction is realized.
Comparative example 4
A certain 5.5 ten thousand tons/year sulfur device is started, and the traditional start method is as follows:
the sulfur production unit adopts gas and air peroxide combustion for heatingThe heating rate is 20 ℃/h, and the gas combustion gas is directly burnt by an incinerator and then discharged by a chimney after passing through a reaction furnace, a waste heat boiler, a primary condenser, a primary heater, a primary reactor, a secondary condenser, a secondary heater, a secondary reactor and a tertiary condenser. When the temperature of a hearth of a reaction furnace is 1000 ℃, the inlet temperature of a primary reactor is 225 ℃, the inlet temperature of a secondary reactor is 215 ℃ and the inlet temperature of a hydrogenation reactor is 220 ℃, the sulfur-making unit switches the acid gas to burn, the acid gas burning gas directly burns through the reaction furnace, a waste heat boiler, a primary condenser, a primary heater, the primary reactor, a secondary condenser, a secondary heater, the secondary reactor and a tertiary condenser and then is discharged through a chimney, and the flue gas SO is discharged through the chimney after directly burning through the burning furnace2The concentration is up to 30000mg/m3Wait for H2S-2SO2And when the temperature is-0.3 ℃, the Claus tail gas of the sulfur production unit can be directly introduced into the tail gas treatment unit, so that the start-up is realized. The energy consumption of the device in the whole start-up period of the start-up process is-88 kg standard oil/ton.
It should be understood that the above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents may be made in the technical solutions described in the foregoing embodiments, or some technical features may be substituted. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A sulfur recovery device filled with a sulfurized hydrogenation catalyst is characterized by comprising a main line, a first overline (20), a second overline (21) and a third overline (22), as well as a delivery pump, a valve and an instrument device for automatic control, which are arranged on a connecting pipeline;
the main line comprises a reaction 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 quench tower (13), an absorption tower (14), an incinerator (16) and a chimney (17) which are sequentially communicated, wherein an air inlet of the reaction furnace (1) is connected with an air inlet (A) and a natural gas inlet (B);
the air inlet of the first cross line (20) is arranged on a connecting pipeline between the three-stage condenser (9) and the tail gas heater (10), and the air outlet of the first cross line (20) is arranged on a connecting pipeline between the absorption tower (14) and the incinerator (16);
the air inlet of the second cross line (21) is arranged on a connecting pipeline between the quenching tower (13) and the absorption tower (14), and the air outlet of the second cross line (21) is arranged on a connecting pipeline between the absorption tower (14) and the incinerator (16);
and the air inlet of the third overline (22) is arranged on a connecting pipeline between the three-stage condenser (9) and the tail gas heater (10), and the air outlet of the third overline (22) is arranged on a connecting pipeline between the steam generator (12) and the quenching tower (13).
2. The sulfur recovery device filled with hydrogenation catalyst in a sulfurized state as defined in claim 1, wherein the rich liquid outlet at the lower part of the absorption tower (14) is connected to the upper part of the regeneration tower (15) through a rich solvent pump (19), and the lean liquid outlet at the lower part of the regeneration tower (15) is connected to the absorbent inlet at the upper part of the absorption tower (14).
3. The start-up method of a sulfur recovery device filled with a hydrogenation catalyst in a sulfurized state according to claim 1 or 2, comprising the steps of:
(1) introducing natural gas and air into the reaction furnace in proportion and burning, adjusting a tube pass valve to enable natural gas burning tail gas to be discharged from the three-stage condenser and then directly enter the quenching tower through a third span line, and then directly enter the incinerator for incineration through a second span line after being discharged from the top of the quenching tower;
(2) when there is no liquid sulfur in the tube pass at the outlet of the three-stage condenser, and/or SO2When the content is less than the set value, the ratio of the introduced natural gas to the introduced air is adjusted to ensure that the natural gas and the air are oxygen-deficient to burn; SO (SO)2The content is 80-100mg/m3The natural gas and the air are mixed according to the ratio of 1: 8.5-9, and oxygen-deficient combustion is carried out;
(3) when the tube pass of the outlet of the three-stage condenser is O2Content, SO2When the content is less than the set value, adjusting a tube pass valve to enable the natural gas combustion tail gas to directly enter the incinerator for incineration from the outlet of the three-stage condenser through a first cross line; o is2The content setting value is 0.2% v/v, SO2The content setting value is 100mg/m3；
(4) After the natural gas combustion tail gas directly enters the incinerator for incineration from the outlet of the three-stage condenser through the first crossover line, the tube side valve is adjusted, and the first crossover line, the second crossover line and the circulating line pipeline are closed, so that the natural gas combustion tail gas enters the incinerator for combustion through the main line;
(5) after the natural gas combustion tail gas enters the incinerator for combustion through the main line, the acid gas is slowly introduced into the reaction furnace, meanwhile, the consumption of the natural gas is reduced, the air quantity is adjusted, and the start-up of the sulfur recovery device is realized.
4. The start-up method of claim 3, wherein before the natural gas is introduced in the step (1), the temperature of the reaction furnace and the incinerator is raised by burning the natural gas at a rate of 10-25 ℃/h; the waste heat boiler, the first-stage condenser, the second-stage condenser and the third-stage condenser are maintained at 120-150 ℃, and the pH value of the quenching water in the quenching tower is maintained at 7-10.
5. The start-up method according to claim 3, wherein in the step (1), the temperature of the hearth of the reaction furnace is 900 ℃ to 1400 ℃, the inlet temperature of the primary reactor is 200 ℃ to 250 ℃, the inlet temperature of the secondary reactor is 200 ℃ to 250 ℃, the inlet temperature of the hydrogenation reactor is 200 ℃ to 250 ℃, and the temperature of the top of the absorption tower is 20 ℃ to 38 ℃.
6. The start-up method according to claim 5, wherein in the step (1), the furnace temperature of the reaction furnace is 1000 ℃ to 1300 ℃, the inlet temperature of the primary reactor is 220 ℃ to 240 ℃, the inlet temperature of the secondary reactor is 210 ℃ to 230 ℃, the inlet temperature of the hydrogenation reactor is 200 ℃ to 230 ℃, and the tower top temperature of the absorption tower is 25 ℃ to 35 ℃.
7. A start-up method according to claim 3, wherein the natural gas and air in step (1) are mixed in a ratio of 1: 10-1: 11 into a reaction furnace.
8. The start-up method of any one of claims 3 to 7, wherein an amine liquid circulation system is established by connecting the absorption tower before the acid gas is introduced into the main line in the step (5).
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