CN106698362A - High-efficiency and energy-saving sulphur recovery device and method - Google Patents
High-efficiency and energy-saving sulphur recovery device and method Download PDFInfo
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- CN106698362A CN106698362A CN201710120066.8A CN201710120066A CN106698362A CN 106698362 A CN106698362 A CN 106698362A CN 201710120066 A CN201710120066 A CN 201710120066A CN 106698362 A CN106698362 A CN 106698362A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2206/00—Waste heat recuperation
- F23G2206/20—Waste heat recuperation using the heat in association with another installation
- F23G2206/203—Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/12—Heat utilisation in combustion or incineration of waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention provides a high-efficiency and energy-saving sulphur recovery device and a high-efficiency energy-saving sulphur recovery method. The sulphur recovery device provided by the invention comprises a thermal reaction system, a Claus reaction system and an exhaust gas incineration and flue gas heat recovery system; a process method of the sulphur recovery device mainly comprises the following steps: performing a thermal reaction and a Claus reaction on an acidic raw gas to produce sulphur and sulphur production exhaust gas, and producing medium-pressure steam as a by-product; feeding the sulphur production exhaust gas into an exhaust gas incineration furnace for incinerating; recovering heat energy from high-temperature flue gas which is produced by the exhaust gas incineration furnace through a flue gas convection chamber, namely, arranging a five-section heat exchange area, including an overheating section, a boiler water supply preheating section, an exhaust gas preheating section, a raw gas preheating section and a sulphur production air preheating section, in the flue gas convection chamber. By using the sulphur recovery device and the sulphur recovery method provided by the invention, the waste heat of the flue gas at the outlet of the exhaust has incineration furnace can be fully utilized; the acidic raw gas, the sulphur production exhaust gas, and sulphur production air can be preheated to a high temperature; the temperature of a sulphur production combustion furnace can be increased; the conversion rate of the sulphur in the furnace is favourably improved; the consumption amount of fuel gas required by the incineration furnace can be reduced.
Description
Technical field
The present invention relates to chemical technology field, and in particular to be a kind of energy-efficient sulfur recovery unit and method, especially
It is that a kind of utilization claus process combines the energy-efficient sulphur recovery to be formed with tail gas burning heat recovery technical optimization
Device and technique.
Background technology
Petroleum chemical industry is an industry for relative highly energy-consuming, and energy-saving having turned into is related to petroleum chemical enterprise or even whole
The big factors of individual industry development.Current national departments concerned has formulated a series of energy-saving and emission-reduction policy, it is determined that future builds up
Index is advanced, meet the energy conservation standard system of national conditions, and main highly energy-consuming trade realizes energy consumption limit standard all standing, more than 80%
Energy efficiency indexes reach advanced world standards.Waste heat, Yu Wen comprehensive utilizations are improved energetically, are to realize that energy-efficient one is important
Approach.
Sulfur recovery unit is typically provided with tail gas burning furnace, for will contain a small amount of H in sulphur tail gas processed2S, COS (carbonyl
Sulphur), the harmful substance such as Sx directly burns and is converted into SO2, remaining H2, the substance combustion such as CO and hydro carbons is into H2O and CO2, high temperature cigarette
Gas directly arranges air or delivers to lower procedure and continues with after reclaiming heat through heat transmission equipment.Due to the H contained by sulphur tail gas processed2S、
H2, the combustible content too low (typically smaller than 3%) such as CO and can not burn, therefore must be heated to sufficiently high temperature can just make this
A little materials produce corresponding conversion.The fuel that usual incinerator needs is provided by the external fuel gas of device, and fuel gas and air are through peace
Loaded on the burner mixed combustion on incinerator, heat is discharged in incinerator combustion chamber, produce high-temperature flue gas, there is provided in sulphur tail gas processed
The energy that the conversion reaction of a small amount of combustible needs.
Sulfur recovery unit belongs to the device of heat surplus, how to make good use of device heat, makes the mutual Proper Match of heat be
Energy-saving key.At present, the tail gas burning furnace of sulfur recovery unit, its combustion chamber produces the temperature of high-temperature flue gas to be generally
650-815 DEG C, the high-temperature flue gas are typically passed through air or produce steam to reclaim heat by waste heat boiler, drop flue-gas temperature
Being entered air or delivered to downstream treatment process by chimney after to 300 DEG C or so carries out deep desulfuration, and its Btu utilization mode is single,
Fume afterheat is underutilized.The sulphur tail gas processed of the tail gas burning furnace entrance of existing claus sulphur recovery units is (general
Be 122-130 DEG C) and air be not all directly entered tail gas burning furnace by preheating, the fuel tolerance for being consumed is larger, operation
It is costly.On the other hand, conventional fume afterheat is used to produce outer defeated low pressure or middle pressure steam, and general full factory's low pressure or middle pressure are steamed
Vapour concentrates by-product by boiler, and quantity of steam is more rich, while for fuel gas, coal steams more economical rationality, therefore,
Sulfur recovery unit need not outer defeated excessive low pressure or middle pressure steam.Additionally, sulfur recovery unit convention acidic unstripped gas and sulphur processed are empty
Gas preheating is main the external middle pressure steam of device or the self-produced middle pressure steam two ways of device, and both preheating methods are except increasing
Outside equipment investment and running cost, preheating temperature is also limit through the steam pressure frequently as thermal source, that is, use the steaming of 4.1MPa
Vapour, also only about 240 DEG C of its preheating temperature.
The content of the invention
It is an object of the invention to provide a kind of energy-efficient sulfur recovery unit and method.Use sulfur recovery of the invention
Device and method can not only make full use of the waste heat of tail gas burning furnace exiting flue gas, and can make acid gas, sulphur tail gas processed, system
Sulphur air preheat can effectively improve burner for producing sulfur temperature to temperature higher, operation is more stablized, and be conducive to improving
Sulphur conversion ratio in stove, and the fuel gas consumption needed for incinerator can be reduced.
To reach above-mentioned purpose, present invention firstly provides a kind of energy-efficient sulfur recovery unit, it includes：Thermal response
System, claus reaction system and tail gas are burned and flue gas heat recovery system；
Wherein, the thermal response system includes：Burner for producing sulfur and waste heat boiler；
The tail gas is burned and flue gas heat recovery system includes：Tail gas burning furnace is connected what is formed with smoke convection room
Body of heater；The smoke convection room is provided with five sections of heat transfer zones, including：Superheat section, boiler feedwater preheating section, tail gas preheating section, original
Material gas preheating section and sulphur air preheat processed section；
Burner for producing sulfur in the thermal response system is connected to waste heat boiler, and the Process Gas outlet of the waste heat boiler is logical
Cross pipeline and be connected to the claus reaction system；
The middle pressure saturated vapor outlet of the waste heat boiler and the steam input pipe line of the superheat section of the smoke convection room
It is connected, so that the flue gas that the middle pressure saturated vapor of waste heat boiler by-product is produced with the tail gas burning furnace is exchanged heat, and will
Vapours is pressed through in after heat exchange outer defeated；
The boiler feedwater efferent duct of the admission port of the waste heat boiler and the boiler feedwater preheating section of the smoke convection room
Line is connected, so that the feedwater of the medium-pressure boiler from battery limit (BL) is exchanged heat with by the flue gas after superheat section heat exchange, and makes preheating
Medium-pressure boiler feedwater afterwards enters waste heat boiler；
The sulphur offgas outlet processed of the claus reaction system is defeated with the tail gas of the tail gas preheating section of the smoke convection room
The one end for entering pipeline is connected, and the other end of the tail gas intake pipeline is connected to the tail gas burning furnace, so that sulphur tail gas processed
Exchanged heat with by the flue gas after the heat exchange of boiler feedwater preheating section, and the sulphur tail gas processed after preheating is entered into tail gas burning furnace
Row is burned；
The acid gas entrance of the burner for producing sulfur is former with the acidity of the unstripped gas preheating section of the smoke convection room
The intake pipeline connection of material gas, so that acid gas are exchanged heat with by the flue gas after the heat exchange of tail gas preheating section, and makes preheating
Acid gas afterwards enter burner for producing sulfur；
The air outlet conduits of the sulphur air preheat processed section of the air intake of the burner for producing sulfur and the smoke convection room
Line is connected, so that air is exchanged heat with by the flue gas after the heat exchange of unstripped gas preheating section, and makes the sulphur air processed after preheating
Into burner for producing sulfur；
The tail gas burning furnace is additionally provided with a fuel gas entrance and an air intake.
Specific embodiment of the invention, it is preferable that the energy-efficient sulfur recovery unit also includes at least one
Platform air blower, the air blower is connected with the air inlet line of the sulphur air preheat processed section of the smoke convection room, for inciting somebody to action
The sulphur air preheat processed section that air is delivered to smoke convection room is exchanged heat with by the flue gas after the heat exchange of unstripped gas preheating section, and
The air after preheating is set to enter burner for producing sulfur.
Specific embodiment of the invention, it is preferable that the energy-efficient sulfur recovery unit also includes at least one
Air-introduced machine and at least a chimney, the chimney pass sequentially through the cigarette that pipeline is connected to the smoke convection room with the air-introduced machine
Gas is exported, for by by the flue gas (flue gas i.e. after heat is reclaimed in five sections of heat transfer zones) after sulphur air preheat processed section heat exchange
Send out battery limit (BL).
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the claus reaction system includes：Pass sequentially through pipe
Two grades of claus reaction devices, three-level claus reaction device and selective catalytic oxidation reactor that line is connected.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is connected with smoke convection room
The body of heater of formation is connected what is formed for vertical incinerator with horizontal smoke convection roomShape body of heater.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is connected with smoke convection room
The body of heater of formation be vertical incinerator withShape smoke convection room is connected what is formedShape body of heater.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is connected with smoke convection room
The body of heater of formation is the horizontal incinerator body of heater to be formed that is connected coaxial with horizontal smoke convection room.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is vertical and cylindrical incinerator.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is vertical type square incinerator.
In above-mentioned energy-efficient sulfur recovery unit, it is preferable that the tail gas burning furnace is horizontal cylinder shape incinerator.
In energy-efficient sulfur recovery unit of the invention, burner for producing sulfur, waste heat boiler, two grades of claus reactions
The concrete structure of the parts such as device, three-level claus reaction device, selective catalytic oxidation reactor can be that this area is conventional,
Do not repeating herein.
On the other hand, present invention also offers a kind of energy-efficient sulfur recovery method, it uses above-mentioned energy-efficient
Sulfur recovery unit, the method comprises the following steps：
(1) acid gas and sulphur air processed is made to be burnt into burner for producing sulfur, combustion product enters waste heat boiler
Saturated vapor is pressed in by-product, then waste heat boiler outlet Process Gas enter claus reaction system, after reaction generate sulphur and
Sulphur tail gas processed；
(2) the middle pressure saturated vapor of by-product into the superheat section of smoke convection room is made, the flue gas produced with tail gas burning furnace
Exchanged heat, and it is outer defeated that vapours will be pressed through in after heat exchange；
(3) medium-pressure boiler from battery limit (BL) is fed water and enter the boiler feedwater preheating section of smoke convection room, overheated with passing through
Flue gas after Duan Huanre is exchanged heat, and the boiler feedwater after preheating is entered waste heat boiler；
(4) make sulphur tail gas processed enter smoke convection room tail gas preheating section, with by boiler feedwater preheating section heat exchange after
Flue gas is exchanged heat, and the sulphur tail gas processed after preheating is entered tail gas burning furnace, while to being passed through fuel gas in tail gas burning furnace
And air, burned with to sulphur tail gas processed；
(5) make acid gas enter smoke convection room unstripped gas preheating section, with by tail gas preheating section heat exchange after
Flue gas is exchanged heat, and the acid gas after preheating is burnt into burner for producing sulfur；
(6) the sulphur air preheat processed section of smoke convection room is admitted air into, with the cigarette after unstripped gas preheating section exchanges heat
Gas is exchanged heat, and the air after preheating is entered burner for producing sulfur for combustion acid unstripped gas；
(7) by by the flue gas (flue gas i.e. after heat is reclaimed in five sections of heat transfer zones) after sulphur air preheat processed section heat exchange
Send out battery limit (BL).
In above-mentioned energy-efficient sulfur recovery method, it is preferable that the pressure of the middle pressure steam of waste heat boiler by-product is 3.5
~4.4MPaG.
In above-mentioned energy-efficient sulfur recovery method, it is preferable that the flue-gas temperature that tail gas burning furnace is produced for 800~
900 DEG C, after the middle pressure steam heat exchange of superheat section and waste heat boiler by-product, the middle pressure superheat steam temperature for obtaining is 420~450
DEG C, the flue-gas temperature after superheat section exchanges heat is 650~700 DEG C.
In above-mentioned energy-efficient sulfur recovery method, it is preferable that the temperature of the medium-pressure boiler feedwater from battery limit (BL) is 104
DEG C~132 DEG C, in boiler feedwater preheating section with after 650~700 DEG C of flue gases after superheat section heat exchange are exchanged heat, obtain
Boiler feed temperature after preheating is 240~260 DEG C, and the flue-gas temperature after boiler feedwater preheating section exchanges heat is 460~500
℃。
In above-mentioned energy-efficient sulfur recovery method, it is preferable that the temperature of sulphur tail gas processed is 122~130 DEG C, in tail gas
After preheating section is exchanged heat with 460~500 DEG C of flue gases after boiler feedwater preheating section exchanges heat, the sulphur processed after the preheating for obtaining
Exhaust temperature is 250~300 DEG C, and the flue-gas temperature after tail gas preheating section exchanges heat is 350~400 DEG C.
In above-mentioned energy-efficient sulfur recovery method, it is preferable that enter the temperature of the acid gas of unstripped gas preheating section
It is 20~40 DEG C to spend, after unstripped gas preheating section is exchanged heat with 350~400 DEG C of flue gases after tail gas preheating section exchanges heat,
Acid gas temperature after the preheating for obtaining is 250~300 DEG C, is by the flue-gas temperature after the heat exchange of unstripped gas preheating section
260~320 DEG C.
In above-mentioned energy-efficient sulfur recovery method, it is preferable that the temperature for entering the air of sulphur air preheat processed section is
Normal temperature, in sulphur air preheat processed section with after 260~320 DEG C of flue gases after the heat exchange of unstripped gas preheating section are exchanged heat, obtains
Preheating after air themperature be 250~300 DEG C, by sulphur air preheat processed section heat exchange after flue-gas temperature be 180~240
℃。
In energy-efficient sulfur recovery method of the invention, burner for producing sulfur, waste heat boiler, two grades of claus reactions
The design parameter of the reaction conducted in the parts such as device, three-level claus reaction device, selective catalytic oxidation reactor and adopt
Catalyst etc. can be that this area is conventional, repeat no more herein.
In energy-efficient sulfur recovery unit of the invention and method, it should be noted that, in the present invention that just brings into operation
Device when, acid gas and air into burner for producing sulfur are the acid gas and air that are not exchanged heat, are treated
Plant running for a period of time, after producing sulphur tail gas processed and high-temperature flue gas, recycles flue gas to acid gas, sulphur air processed and system
Sulphur tail gas etc. is exchanged heat, and the acid gas after heat exchange, sulphur air processed are sent into burner for producing sulfur.
The present invention provide energy-efficient sulfur recovery unit mainly include thermal response system, claus reaction system and
Tail gas is burned and flue gas heat recovery system；The energy-efficient sulfur recovery method that the present invention is provided is mainly included the following steps that：
There is thermal response and claus reaction production sulphur and sulphur tail gas processed, and by-product middle pressure steam in acid gas；Sulphur tail gas processed send
The tail gas burning furnace entered in tail gas burning and flue gas heat recovery system is burned；The high-temperature flue gas warp that tail gas burning furnace is produced
Heat energy is reclaimed in smoke convection room in tail gas burning and flue gas heat recovery system, i.e., set five sections of heat exchange in smoke convection room
Area, mainly including superheat section, boiler feedwater preheating section, tail gas preheating section, unstripped gas preheating section and sulphur air preheat processed section.
Compared with prior art, the present invention has advantages below：
(1) first by the acid gas in Crouse's recovery technology of sulfur, sulphur air processed, sulphur tail gas material processed preheating collection
Into in the smoke convection room after tail gas burning furnace, rationally using the different potential temperature heats of flue gas, fume afterheat obtains abundant profit
With.
(2) device efficiency is high, and technological process is simple, and equipment investment is low, takes up an area and saves, and technological process is short, technical process safety
It is reliable, in the absence of dangerous larger technique or equipment.
(3) tail gas burning furnace not byproduct steam, the logistics for needing to heat is supplied to using this part of waste heat, has saved device
Fuel gas is consumed.
In sum, tail gas burning furnace exiting flue gas can not only be made full use of using sulfur recovery unit of the invention and method
Waste heat, and acid gas, sulphur tail gas processed, sulphur air preheat processed to temperature higher can be made；It is effectively improved sulphur combustion processed
The temperature of stove is burnt, operation is more stablized, be conducive to improving sulphur conversion ratio in stove, and needed for significantly reducing incinerator
Fuel gas consumption；Overcome the fuel that existing burning outlet of still high-temperature flue gas heat is not made full use of or byproduct steam is caused
Waste, and acid gas and the low limitation of sulphur air preheating temperature processed；And then can save energy, reduce operating cost,
Equipment investment is reduced, shortened technological process, improved device efficiency.
Brief description of the drawings
Fig. 1 is the energy-efficient sulfur recovery unit structure and process flow diagram that embodiment 1 is provided；
Fig. 2 is the energy-efficient sulfur recovery unit structure and process flow diagram that embodiment 2 is provided；
Fig. 3 is the energy-efficient sulfur recovery unit structure and process flow diagram that embodiment 3 is provided；
Primary clustering symbol description：
1- burner for producing sulfur；2- waste heat boilers；Bis- grades of claus reaction devices of 3-；4- three-level claus reaction devices；5- is selected
Property catalyst oxidation reactor；6- tail gas burning furnaces；7- smoke convections room；8- superheat sections；9- boiler feedwater preheating sections；10- tail gas
Preheating section；11- unstripped gas preheating sections；12- sulphur air preheat section；13- air blowers；14- air-introduced machines；15- chimneys.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, in conjunction with detail below
Embodiment and Figure of description technical scheme is carried out it is described further below, but it is not intended that to it is of the invention can
The restriction of practical range.
Embodiment 1
A kind of energy-efficient sulfur recovery unit is present embodiments provided, as shown in figure 1, it includes：Thermal response system, gram
Louth reaction system, tail gas are burned and flue gas heat recovery system, air blower 13, air-introduced machine 14 and chimney 15；
Wherein, the thermal response system includes：Burner for producing sulfur 1 and waste heat boiler 2；
The claus reaction system includes：Two grades of claus reaction devices 3, three-level claus reaction device 4 and selectivity
Catalyst oxidation reactor 5；
The tail gas is burned and flue gas heat recovery system includes：Tail gas burning furnace 6 is connected to be formed with smoke convection room 7
Body of heater, the body of heater is connected what is formed for vertical incinerator with horizontal smoke convection roomShape body of heater, the vertical burning
Stove is vertical and cylindrical incinerator；The smoke convection room 7 is provided with five sections of heat transfer zones, including：Superheat section 8, boiler feedwater is pre-
Hot arc 9, tail gas preheating section 10, unstripped gas preheating section 11 and sulphur air preheat processed section 12；
Burner for producing sulfur 1 in the thermal response system is connected to waste heat boiler 2, and the Process Gas of the waste heat boiler 2 go out
Mouthful by pipeline be sequentially connected to two grades of claus reaction devices 3 of the claus reaction system, three-level claus reaction device 4 with
And selective catalytic oxidation reactor 5；
The middle pressure saturated vapor outlet of the waste heat boiler 2 and the steam input pipe of the superheat section 8 of the smoke convection room 7
Line is connected, so that the flue gas that the middle pressure saturated vapor of the by-product of waste heat boiler 2 is produced with the tail gas burning furnace 6 is exchanged heat,
And it is outer defeated that vapours will be pressed through in after heat exchange；
The admission port of the waste heat boiler 2 exports with the boiler feedwater of the boiler feedwater preheating section 9 of the smoke convection room 7
Pipeline is connected, so that the feedwater of the medium-pressure boiler from battery limit (BL) is exchanged heat with by the flue gas after the heat exchange of superheat section 8, and makes pre-
Boiler feedwater after heat enters waste heat boiler 2；
The sulphur offgas outlet processed of the claus reaction system and the tail gas of the tail gas preheating section 10 of the smoke convection room 7
One end of intake pipeline is connected, and the other end of the tail gas intake pipeline is connected to the tail gas burning furnace 6, so that sulphur tail processed
Gas is exchanged heat with by the flue gas after the heat exchange of boiler feedwater preheating section 9, and the sulphur tail gas processed after preheating is burned into tail gas
Stove 6 is burned；
The acid of the acid gas entrance of the burner for producing sulfur 1 and the unstripped gas preheating section 11 of the smoke convection room 7
Property the connection of unstripped gas intake pipeline so that acid gas are exchanged heat with the flue gas after tail gas preheating section 10 exchanges heat, and
The acid gas after preheating are made to enter burner for producing sulfur 1；
The air intake of the burner for producing sulfur 1 is defeated with the air of the sulphur air preheat processed section 12 of the smoke convection room 7
Go out pipeline to be connected, so that sulphur air processed is exchanged heat with by the flue gas after the heat exchange of unstripped gas preheating section 11, and after making preheating
Air enter burner for producing sulfur 1；
The chimney 15 passes sequentially through the exhanst gas outlet that pipeline is connected to the smoke convection room 7 with the air-introduced machine 14,
For will be sent out by the flue gas (flue gas i.e. after heat is reclaimed in five sections of heat transfer zones) after the heat exchange of sulphur air preheat processed section 12
Battery limit (BL)；
The tail gas burning furnace 6 is additionally provided with a fuel gas entrance and an air intake.
The present embodiment additionally provides a kind of energy-efficient sulfur recovery method, and it uses above-mentioned device, as shown in figure 1,
As a example by producing sulphur amount for 20,000 tons/year, the method is comprised the following steps：
(1) acid gas are made to be burnt into burner for producing sulfur 1 with air, subsequently into the by-product 3.5 of waste heat boiler 2
After the middle pressure steam of~4.4MPaG, the Process Gas of the output of waste heat boiler 2 sequentially enter two grades of grams of labor in claus reaction system
This reactor 3, three-level claus reaction device 4 and selective catalytic oxidation reactor 5, generate sulphur and sulphur tail processed after reaction
Gas；
(2) 3.5~4.4MPaG middle pressure steams of by-product into the superheat section 8 of smoke convection room 7 are made, with tail gas burning furnace 6
The 800 DEG C of flue gases for producing are exchanged heat, and the middle pressure superheat steam temperature for obtaining is 420 DEG C, the flue gas after the heat exchange of superheat section 8
Temperature is 650 DEG C, vapours will be pressed through in after heat exchange outer defeated；
(3) 132 DEG C of medium-pressure boilers from battery limit (BL) is fed water and enter the boiler feedwater preheating section 9 of smoke convection room 7, with warp
The 650 DEG C of flue gases crossed after superheat section 8 exchanges heat are exchanged heat, and the boiler feed temperature after the preheating for obtaining is 253 DEG C, by boiler
Flue-gas temperature after the heat exchange of feed-water preheating section 9 is 460 DEG C, the boiler feedwater after preheating is entered waste heat boiler 2；
(4) make 122 DEG C of sulphur tail gas processed into the tail gas preheating section 10 of smoke convection room 7, preheated with by boiler feedwater
460 DEG C of flue gases after the heat exchange of section 9 are exchanged heat, and the sulphur exhaust temperature processed after the preheating for obtaining is 280 DEG C, by tail gas preheating section
Flue-gas temperature after 10 heat exchange is 360 DEG C, and the sulphur tail gas processed after preheating is entered tail gas burning furnace 6, while passing through fuel gas
Entrance to being passed through fuel gas (i.e. natural gas) in tail gas burning furnace 6 and by air intake to being passed through air in tail gas burning furnace 6,
Burned with to sulphur tail gas processed；
(5) make 20~40 DEG C acid gas enter smoke convection room 7 unstripped gas preheating section 11, it is pre- with by tail gas
360 DEG C of flue gases after hot arc 10 exchanges heat are exchanged heat, and the acid gas temperature after the preheating for obtaining is 280 DEG C, by raw material
Flue-gas temperature after gas preheating section 11 exchanges heat is 266 DEG C, the acid gas after preheating is fired into burner for producing sulfur 1
Burn；
(6) normal temperature air from air blower 13 is made to enter the sulphur air preheat processed section 12 of smoke convection room 7, it is former with passing through
266 DEG C of flue gases after material gas preheating section 11 exchanges heat are exchanged heat, and the air themperature after the preheating for obtaining is 280 DEG C, by sulphur processed
Flue-gas temperature after the heat exchange of air preheat section 12 is 180 DEG C, and the air after preheating is entered burner for producing sulfur 1 is used for combustion acid
Unstripped gas；
(7) by 180 DEG C of flue gases after sulphur air preheat processed section 12 exchanges heat (i.e. after heat is reclaimed in five sections of heat transfer zones
Flue gas) battery limit (BL) is sent out by air-introduced machine 14 and chimney 15.
In the energy-efficient sulfur recovery unit and method that the present embodiment is provided, it should be noted that, brought into operation just
During the device of the present embodiment, into burner for producing sulfur acid gas and air be the acid gas that are not exchanged heat with
Air, treats plant running for a period of time, after producing sulphur tail gas processed and high-temperature flue gas, recycles flue gas to acid gas, sulphur processed
Air and sulphur tail gas processed etc. are exchanged heat, and by the acid gas after heat exchange, sulphur air processed feeding burner for producing sulfur.
Embodiment 2
Present embodiments provide a kind of energy-efficient sulfur recovery unit and method, as shown in Fig. 2 the structure of the device and
Technological process is substantially the same manner as Example 1, and difference is：Tail gas burning furnace 6 is connected the stove to be formed with smoke convection room 7
Body be vertical incinerator withShape smoke convection room is connected what is formedShape body of heater, the vertical incinerator is vertical type square
Shape incinerator.
Embodiment 3
Present embodiments provide a kind of energy-efficient sulfur recovery unit and method, as shown in figure 3, the structure of the device and
Technological process is substantially the same manner as Example 1, and difference is：Tail gas burning furnace 6 is connected the stove to be formed with smoke convection room 7
Body is the horizontal incinerator body of heater to be formed that is connected coaxial with horizontal smoke convection room, and the horizontal incinerator burns for horizontal cylinder shape
Burn stove.
Claims (9)
1. a kind of energy-efficient sulfur recovery unit, it includes：Thermal response system, claus reaction system and tail gas burn and
Flue gas heat recovery system；
Wherein, the thermal response system includes：Burner for producing sulfur and waste heat boiler；
The tail gas is burned and flue gas heat recovery system includes：Tail gas burning furnace is connected the stove to be formed with smoke convection room
Body；The smoke convection room is provided with five sections of heat transfer zones, including：Superheat section, boiler feedwater preheating section, tail gas preheating section, raw material
Gas preheating section and sulphur air preheat processed section；
Burner for producing sulfur in the thermal response system is connected to waste heat boiler, and the Process Gas outlet of the waste heat boiler is by pipe
Line is connected to the claus reaction system；
The middle pressure saturated vapor outlet of the waste heat boiler is connected with the steam input pipe line of the superheat section of the smoke convection room
Connect, so that the flue gas that the middle pressure saturated vapor of waste heat boiler by-product is produced with the tail gas burning furnace is exchanged heat, and will heat exchange
Vapours is pressed through in afterwards outer defeated；
The boiler feedwater export pipeline phase of the admission port of the waste heat boiler and the boiler feedwater preheating section of the smoke convection room
Connection, so that the feedwater of the medium-pressure boiler from battery limit (BL) is exchanged heat with the flue gas after superheat section exchanges heat, and after making preheating
Medium-pressure boiler feedwater enters waste heat boiler；
The sulphur offgas outlet processed of the claus reaction system and the tail gas input pipe of the tail gas preheating section of the smoke convection room
One end of line is connected, and the other end of the tail gas intake pipeline is connected to the tail gas burning furnace, so that sulphur tail gas processed and warp
The flue gas crossed after the heat exchange of boiler feedwater preheating section is exchanged heat, and the sulphur tail gas processed after preheating is burnt into tail gas burning furnace
Burn；
The acid gas of the acid gas entrance of the burner for producing sulfur and the unstripped gas preheating section of the smoke convection room
Intake pipeline is connected, so that acid gas are exchanged heat with the flue gas after tail gas preheating section exchanges heat, and after making preheating
Acid gas enter burner for producing sulfur；
The air outlet line phase of the sulphur air preheat processed section of the air intake of the burner for producing sulfur and the smoke convection room
Connection, so that air is exchanged heat with by the flue gas after the heat exchange of unstripped gas preheating section, and enters the sulphur air processed after preheating
Burner for producing sulfur；
The tail gas burning furnace is additionally provided with a fuel gas entrance and an air intake.
2. sulfur recovery unit energy-efficient according to claim 1, it also includes at least one air blower, the air blower
The air inlet line of the sulphur air preheat processed section with the smoke convection room is connected, for delivering the air to smoke convection room
Sulphur air preheat processed section with by unstripped gas preheating section heat exchange after flue gas exchanged heat, and make the air after preheating enter make
Sulphur burner.
3. energy-efficient sulfur recovery unit according to claim 1 or claim 2, it also includes an at least air-introduced machine and at least one
Chimney, the chimney passes sequentially through the exhanst gas outlet that pipeline is connected to the smoke convection room with the air-introduced machine, for will be through
The flue gas crossed after sulphur air preheat section heat exchange processed sends out battery limit (BL).
4. sulfur recovery unit energy-efficient according to claim 1, wherein, the claus reaction system includes：Successively
Two grades of claus reaction devices, three-level claus reaction device and the selective catalytic oxidation reactor connected by pipeline.
5. sulfur recovery unit energy-efficient according to claim 1, wherein, the tail gas burning furnace and smoke convection room phase
The body of heater for being formed is connected for vertical incinerator is connected what is formed with horizontal smoke convection roomShape body of heater,
Or for vertical incinerator withShape smoke convection room is connected what is formedShape body of heater,
Or the body of heater to be formed that is connected for horizontal incinerator is coaxial with horizontal smoke convection room.
6. sulfur recovery unit energy-efficient according to claim 1 or 5, wherein, the tail gas burning furnace is vertical cylinder
Shape incinerator, vertical type square incinerator or horizontal cylinder shape incinerator.
7. a kind of energy-efficient sulfur recovery method, it uses the energy-efficient sulphur any one of claim 1-6 to return
Receiving apparatus, the method is comprised the following steps：
(1) acid gas and sulphur air processed is made to be burnt into burner for producing sulfur, combustion product enters waste heat boiler by-product
Middle pressure saturated vapor, the Process Gas that then waste heat boiler is exported enter claus reaction system, and sulphur and sulphur processed are generated after reaction
Tail gas；
(2) the middle pressure saturated vapor of by-product into the superheat section of smoke convection room is made, the flue gas produced with tail gas burning furnace is carried out
Heat exchange, and it is outer defeated that vapours will be pressed through in after heat exchange；
(3) medium-pressure boiler from battery limit (BL) is fed water and enter the boiler feedwater preheating section of smoke convection room, changed with by superheat section
Flue gas after heat is exchanged heat, and the boiler feedwater after preheating is entered waste heat boiler；
(4) sulphur tail gas processed is made to enter the tail gas preheating section of smoke convection room, with the flue gas after boiler feedwater preheating section exchanges heat
Exchanged heat, and the sulphur tail gas processed after preheating is entered tail gas burning furnace, while to being passed through fuel gas and sky in tail gas burning furnace
Gas, burns with to sulphur tail gas processed；
(5) acid gas are made to enter the unstripped gas preheating section of smoke convection room, with the flue gas after tail gas preheating section exchanges heat
Exchanged heat, and the acid gas after preheating is burnt into burner for producing sulfur；
(6) the sulphur air preheat processed section of smoke convection room is admitted air into, is entered with by the flue gas after the heat exchange of unstripped gas preheating section
Row heat exchange, and the air after preheating is entered burner for producing sulfur for combustion acid unstripped gas；
(7) battery limit (BL) will be sent out by the flue gas after sulphur air preheat processed section heat exchange.
8. energy-efficient sulfur recovery method according to claim 7, wherein, the pressure of the middle pressure steam of waste heat boiler by-product
Power is 3.5~4.4MPaG.
9. energy-efficient sulfur recovery method according to claim 7, wherein, the flue-gas temperature that tail gas burning furnace is produced is
800~900 DEG C, after the middle pressure steam heat exchange of superheat section and waste heat boiler by-product, the middle pressure superheat steam temperature for obtaining is 420
~450 DEG C, the flue-gas temperature after superheat section exchanges heat is 650~700 DEG C；
The temperature of the medium-pressure boiler feedwater from battery limit (BL) is 104 DEG C~132 DEG C, is changed with by superheat section in boiler feedwater preheating section
After 650~700 DEG C of flue gases after heat are exchanged heat, the boiler feed temperature after the preheating for obtaining is 240~260 DEG C, by pot
Flue-gas temperature after the section heat exchange of stove feed-water preheating is 460~500 DEG C；
The temperature of sulphur tail gas processed is 122~130 DEG C, 460 in tail gas preheating section and after boiler feedwater preheating section exchanges heat~
After 500 DEG C of flue gases are exchanged heat, the sulphur exhaust temperature processed after the preheating for obtaining is 250~300 DEG C, is exchanged heat by tail gas preheating section
Flue-gas temperature afterwards is 350~400 DEG C；
Temperature into the acid gas of unstripped gas preheating section is 20~40 DEG C, is preheated with by tail gas in unstripped gas preheating section
After 350~400 DEG C of flue gases after Duan Huanre are exchanged heat, the acid gas temperature after the preheating for obtaining is 250~300 DEG C,
Flue-gas temperature after unstripped gas preheating section exchanges heat is 260~320 DEG C；
Temperature into the air of sulphur air preheat processed section is normal temperature, is changed with by unstripped gas preheating section in sulphur air preheat processed section
After 260~320 DEG C of flue gases after heat are exchanged heat, the air themperature after the preheating for obtaining is 250~300 DEG C, empty by sulphur processed
Flue-gas temperature after the heat exchange of gas preheating section is 180~240 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107830538A (en) * | 2017-12-07 | 2018-03-23 | 南京宜热纵联节能科技溧阳有限公司 | The indirect type catalytic burning smoke multistage heat-exchange system and technique of a kind of optimization |
| CN108786370A (en) * | 2018-06-27 | 2018-11-13 | 山东大学 | It burns, the Sulphur ressource recovery method and device of parsing, carbon heat reducing coordination |
| CN109911863A (en) * | 2019-04-23 | 2019-06-21 | 中国海洋石油集团有限公司 | A kind of Sulfur Recovery Equipment |
| CN110056890A (en) * | 2019-02-27 | 2019-07-26 | 洛阳瑞昌环境工程有限公司 | A kind of high-sulfur exhaust treatment system and technique |
| CN114735657A (en) * | 2022-04-22 | 2022-07-12 | 瑞切尔石化工程(上海)有限公司 | Condenser for sulfur production device, sulfur production device based on Claus method and sulfur production process |
| CN115959633A (en) * | 2021-10-09 | 2023-04-14 | 中石化南京化工研究院有限公司 | Startup temperature rising system and startup temperature rising method of sulfuric acid preparation device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1519529A (en) * | 2003-09-02 | 2004-08-11 | 肖国雄 | Equipment for recovering multistaged waste heat of gas in flue |
| CN201052968Y (en) * | 2007-03-08 | 2008-04-30 | 四川四维工程设计有限公司 | Low-temperature Claus sulfur reclaiming device |
| CN101586918A (en) * | 2009-06-24 | 2009-11-25 | 哈尔滨金鑫电气有限责任公司 | The multi-stage waste heat recovery device of industrial furnace high-temperature flue gas |
| CN103318847A (en) * | 2013-07-08 | 2013-09-25 | 中石化南京工程有限公司 | High-efficiency sulfur recovery method of waste gas containing hydrogen sulfide |
| CN204237559U (en) * | 2014-10-30 | 2015-04-01 | 中国石油化工股份有限公司 | A kind of Acidic Gas Treating system |
-
2017
- 2017-03-02 CN CN201710120066.8A patent/CN106698362B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1519529A (en) * | 2003-09-02 | 2004-08-11 | 肖国雄 | Equipment for recovering multistaged waste heat of gas in flue |
| CN201052968Y (en) * | 2007-03-08 | 2008-04-30 | 四川四维工程设计有限公司 | Low-temperature Claus sulfur reclaiming device |
| CN101586918A (en) * | 2009-06-24 | 2009-11-25 | 哈尔滨金鑫电气有限责任公司 | The multi-stage waste heat recovery device of industrial furnace high-temperature flue gas |
| CN103318847A (en) * | 2013-07-08 | 2013-09-25 | 中石化南京工程有限公司 | High-efficiency sulfur recovery method of waste gas containing hydrogen sulfide |
| CN204237559U (en) * | 2014-10-30 | 2015-04-01 | 中国石油化工股份有限公司 | A kind of Acidic Gas Treating system |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107830538A (en) * | 2017-12-07 | 2018-03-23 | 南京宜热纵联节能科技溧阳有限公司 | The indirect type catalytic burning smoke multistage heat-exchange system and technique of a kind of optimization |
| CN108786370A (en) * | 2018-06-27 | 2018-11-13 | 山东大学 | It burns, the Sulphur ressource recovery method and device of parsing, carbon heat reducing coordination |
| CN110056890A (en) * | 2019-02-27 | 2019-07-26 | 洛阳瑞昌环境工程有限公司 | A kind of high-sulfur exhaust treatment system and technique |
| CN109911863A (en) * | 2019-04-23 | 2019-06-21 | 中国海洋石油集团有限公司 | A kind of Sulfur Recovery Equipment |
| CN115959633A (en) * | 2021-10-09 | 2023-04-14 | 中石化南京化工研究院有限公司 | Startup temperature rising system and startup temperature rising method of sulfuric acid preparation device |
| CN114735657A (en) * | 2022-04-22 | 2022-07-12 | 瑞切尔石化工程(上海)有限公司 | Condenser for sulfur production device, sulfur production device based on Claus method and sulfur production process |
| CN114735657B (en) * | 2022-04-22 | 2024-06-07 | 瑞切尔石化工程(上海)有限公司 | Condenser for sulfur production device, sulfur production device based on Claus method and sulfur production process |
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