CN109650346A - A kind of wet process sulfur process system and method for the secondary pressurized production concentrated sulfuric acid - Google Patents
A kind of wet process sulfur process system and method for the secondary pressurized production concentrated sulfuric acid Download PDFInfo
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- CN109650346A CN109650346A CN201910071690.2A CN201910071690A CN109650346A CN 109650346 A CN109650346 A CN 109650346A CN 201910071690 A CN201910071690 A CN 201910071690A CN 109650346 A CN109650346 A CN 109650346A
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 321
- 238000000034 method Methods 0.000 title claims abstract description 205
- 230000008569 process Effects 0.000 title claims abstract description 132
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 28
- 239000011593 sulfur Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 198
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000002485 combustion reaction Methods 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 55
- 239000003595 mist Substances 0.000 claims abstract description 42
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000000443 aerosol Substances 0.000 claims abstract description 7
- 239000012717 electrostatic precipitator Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 56
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- 238000009833 condensation Methods 0.000 claims description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
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- 239000002737 fuel gas Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
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- 238000005516 engineering process Methods 0.000 description 11
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- 230000007423 decrease Effects 0.000 description 4
- 238000011143 downstream manufacturing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
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- 239000010959 steel Substances 0.000 description 3
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 238000006477 desulfuration reaction Methods 0.000 description 2
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- 238000002309 gasification Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- 239000002351 wastewater Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 231100000618 neurotoxin Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of wet process sulfur process system and method for secondary pressurized production concentrated sulfuric acid, and process system includes H2S burner, the combination type reactor being attached thereto, sulfuric acid vapor condenser, acid mist eliminator and tail gas washing tower；H2S burner is used to hydrogen sulfide sour gas burning into SO2Process gas, combination type reactor are used for SO2Process gas catalysis oxidation generates SO3Process gas；Sulfuric acid vapor condenser is used for SO3Process gas condenses to form sulfuric acid, and bottom also passes through combustion air fan and H2S burner is connected；Acid mist eliminator is connect with sulfuric acid vapor condenser, for trapping the sulfuric acid aerosol of abjection entrainment；The top of acid mist eliminator is also connect with tail gas washing tower, and the top gas outlet of tail gas washing tower is also successively arranged electrostatic precipitator and exhaust fan, and exhaust fan after tail gas pressurizes for being discharged.Technique of the invention compares more traditional wet process sulfur process, and superheated steam yield is bigger, energy consumption is lower.
Description
Technical field
The present invention relates to a kind of wet process sulfur process system and method for secondary pressurized production concentrated sulfuric acid.
Background technique
H2S is one of the by-product generated during the fossil energies such as coal, natural gas and petrochemical industry utilize, in coalification
A large amount of hydrogen sulfide can be all generated in the generating process of work, gas chemical industry and petrochemical industry.Hydrogen sulfide be it is a kind of it is colourless have it is smelly
The hypertoxic gas of egg odor, is strong neurotoxin, has intense stimulus effect to respiratory mucosa.
H2S acid waste gas not directly discharges environment.H at present2There are mainly two types of the Land use systems of S acid waste gas: one is
Crouse produces sulphur；Another is to produce the concentrated sulfuric acid by wet process relieving haperacidity technology.However traditional wet process relieving haperacidity technology is deposited
The energy dissipation the problem of, and electric quantity consumption is also larger.Due to the strong corrosive feature of wet process acid making system, contain deep-etching
Property process gas there are problems that leakage.These all become wet process acid-making process problem to be solved.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome existing for wet process acid-making process in the prior art energy consumption is high,
The defect easily leaked, and provide a kind of wet process sulfur process system and method for secondary pressurized production concentrated sulfuric acid.The present invention mentions
The technique of confession is a kind of by secondary pressurized wet process sulfuric acid new process, will contain H2S sour gas is by burning, catalyzed conversion production is dense
Sulfuric acid.It is bigger compared to more traditional wet process sulfur process superheated steam yield, energy consumption is lower.
The present invention provides a kind of wet process sulfur process system of secondary pressurized production concentrated sulfuric acid, the wet process sulfur processes
System includes a H2S burner, one and the H2The connected combination type reactor of S burner, a sulfuric acid vapor condenser,
One acid mist eliminator and a tail gas washing tower；
The H2S burner, which is used to burn hydrogen sulfide sour gas, generates SO2Process gas, the combination type reactor are used
In by SO2Process gas catalysis oxidation generates SO3The inside of process gas, the combination type reactor is equipped with several catalyst beds
And the sect heat-exchanger being distributed between the two neighboring catalyst bed；
The sulfuric acid vapor condenser is used for SO3Process gas condenses to form sulfuric acid, and the sulfuric acid vapor condenser includes
The top of one shell, the shell is equipped with an exhaust port, has an input SO in the bottom of the shell3Process gas
Air inlet is additionally provided with a leakage fluid dram below the air inlet, and the long axis direction in the shell along the shell is equipped with
If for the stem glass tube for the cold air that circulates, the glass tube is located between the two sidewalls of the shell, the glass tube
Positioned at the cold air upstream one end be head end, positioned at the cold air downstream one end be tail end, the cold air upstream and
The adjacent glass tube is connected to end to form the cold air flow passage of at least one one-way guide flow between downstream；The sulphur
The bottom of acid vapor condenser also passes through a combustion air fan and the H2S burner is connected, and the combustion air fan is used for institute
The H is delivered to after stating the hot-air pressurization of the bottom discharge of sulfuric acid vapor condenser2S burner；
The acid mist eliminator is connect with the sulfuric acid vapor condenser, and junction is set to the air inlet and the tail gas
On shell between discharge outlet, for trapping the sulfuric acid aerosol of abjection entrainment；
The top of the acid mist eliminator is also connect with the tail gas washing tower, and the top gas of the tail gas washing tower goes out
Mouth is also successively arranged an electrostatic precipitator and an exhaust fan, and the exhaust fan after tail gas pressurizes for being discharged.
Preferably, the H2S burner has a burner, and there is the burner central passage and ring to be located in described
A circular passage outside heart channel, the central passage is for being passed through H2The mixed gas of S sour gas and air, the annular are logical
Road is for being passed through fuel gas.Using sour gas cofiring technology, the i.e. burner of special designing, sour gas is sent into hole pulse in its center
With air burning, while fuel gas improves the stability of sour gas burning by the aftercombustion of burner ring system, which solves
H in sour gas2S fluctuation of concentration is big, ensures in H2S concentration is under 1% or more low concentration (such as 4%-15%mol) operating condition
Stablize reaction.Burner Load Regulation speed is fast, adaptable, and gasification efficiency is high.
In the present invention, the H2S burner is preferably a combustion furnace, and swirl flow device is provided in burner hearth.
Wherein, waste heat boiler of the combustion furnace preferably also with a downstream is directly connected to, the gas of the waste heat boiler
Body outlet is also connect with the top of the combination type reactor.Heat technologic gas after burning is directly entered described by combustion furnace
The entrance tube side of waste heat boiler enters the combination type reactor from top after cooling down.Combustion furnace and downstream waste heat boiler are straight
It connects in succession, using direct heat transfer technology, heat recovery efficiency is high, overcomes the defect of equipment easy fouling and blocking.
Wherein, preferably, the heat transferring medium exit of the waste heat boiler also presses drum to connect with one, outlet setting is steamed
Vapour superheater in steam superheater, presses steam superheating with the heat centering of hot-air.By the outlet temperature for adjusting waste heat boiler
To adjust the temperature after steam superheating.The steam quality outside battery limit (BL) can be gone out with stable feeding by steam superheater, meet steam pipe
Net requires.
Preferably, the inside of the combination type reactor be equipped with 3 catalyst beds and 2 sect heat-exchangers, described section
Between heat exchanger be sequentially distributed between the two neighboring catalyst bed.It is denoted as the first catalyst bed, first from top to bottom
Sect heat-exchanger, the second catalyst bed, the second sect heat-exchanger and third catalyst bed.The catalyst bed is filled with
Catalyst, the top of each catalyst bed set manhole, and lower part sets catalyst discharge port.Under the action of catalyst, SO2It is catalyzed oxygen
Change is converted into SO3, the excessive combustion air of combustion reaction section helps to improve SO2Reaction equilibrium conversion.Combined type reaction
Device is compact-sized, save the cost, optimizes space layout, convenient for manufacture maintenance, and is conducive to the recycling of thermal energy gradient, science
Rationally.
Sect heat-exchanger bottom and housing parts are fixed using steel channel beam；It is adopted at the top of sect heat-exchanger with housing parts
It is attached with conical shell, connection type guarantees the free extension of sect heat-exchanger using being slidably connected；Sect heat-exchanger and shell
Connected adapter tube should have enough length, keep certain flexibility, prevent from generating shell excessive local stress.
Wherein, process gas is entered by the entrance on combination type reactor top, into the first catalyst bed.Gas passes through
After catalyst bed, Partial Conversion is completed, the hot gas after reaction passes through the flase floor of bed lower part.It is successively spread above flase floor
If the double-deck silk screen of 10*10mm- string diameter Φ 2mm, 25 millimeters of porcelain balls of Φ of H=75mm, the double-deck silk of 3*3mm- string diameter Φ 1mm
Net prevents catalyst breakage from falling into next sheaf space.Process gas passes through flase floor, enters the first sect heat-exchanger by conical shell；
Sect heat-exchanger uses coiled pipe structure, and centre is using three pieces of support plate supports, to guarantee free extension, heat exchanger tube and support plate
It does not weld, keeps being slidably connected；The outside of heat exchanger tube is sealed with stainless steel plate, prevents process gas from passing through between heat exchanger tube and support plate
Gap.And so on, process gas passes sequentially through the second catalyst bed, the second sect heat-exchanger, after third catalyst bed,
It is flowed out from the lower outlet of combination type reactor.
Wherein, the bottom of the combination type reactor is preferably also provided with a technique Gas Cooler.
In sulfuric acid vapor condenser of the present invention, the cold air channel of the one-way guide flow formed by glass tube be can be resistant to
By high temperature and deep-etching, so that it is guaranteed that in long-time use the fluency of cold air and heat exchanger safety.Above-mentioned glass
Pipe can use borosilicate glass tube, quartz glass or other high temperature resistant deep-etching glass.
A fiber filter plate is preferably also provided at the top of the sulfuric acid vapor condenser.The acid mist eliminator is preferably
One high-speed fibre demister.The method trapped by high-efficiency fiber demister physics realizes the efficient process to acid mist, demisting effect
Rate >=95%, pressure drop is small (≤1.0KPa), does not influence exhaust emissions.The high-speed fibre demister preferably uses high-intensitive
Fibre cleavages silk wraps up the filter screen of PTFE, is woven to layered filter, when the process gas containing sulfuric acid droplets (acid mist) passes through
When the filter, intercepted by forcing, the efficient trapping for the sulfuric acid aerosol that realization is carried secretly to acid mist and wherein, then tail gas is arranged
It is vented to chimney, filtering accuracy is up to 99.99% (>=0.5um).
Technique of the invention eliminates the operation of the external imported technology combusting silicone oil manufacture nuclei of condensation, is removed by high-efficiency fiber
The method of day with fog physics trapping, the same efficient process realized to acid mist.Control of acid fog forces interception mode using Multi-stage precise,
Outlet acid mist≤10ppm is directly controlled under any operating condition.
Wherein, it (is introduced technology instead of foreign countries by the interior fiber filter plate set and external high-speed fibre demister cooperation
The purpose of operation of the combusting silicone oil manufacture nuclei of condensation, the operation is enhancing sulfuric acid vapor condensation, and it is dense to reduce sulfuric acid aerosol in tail gas
Degree), the sulfuric acid mist carried secretly in gas is removed, higher sulfuric acid mist capture rate is can achieve, is substantially free of in emptying end gas
Acid mist also can guarantee acid mist qualified discharge in tail gas even if there is micro acid mist.
In the present invention, preferably, the leakage fluid dram is also connect with a sulfuric acid blending tank in the sulfuric acid vapor condenser.
It should be noted that the axis extending direction of the cylindrical body is the shell when above-mentioned shell is a cylindrical body
The long axis direction of body, and it is the side wall that cylindrical body, which is formed by surface then around axis convolution,.
In addition, the head end and tail end of the glass tube can be respectively positioned on the enclosure interior, the initial and end of the glass tube at this time
It is connected by the glass pipe of adaptation.It with no restrictions to the shape for being formed by cold air flow passage at this, can be " bow " word
Type, " Z " font or other shapes.
In the sulfuric acid vapor condenser, the flow direction design for the characteristic of cooperation cold air decline, upper entering and lower leaving can be into one
Step improves the mobility of cold air, improves velocity of medium, then improves condensation efficiency.
In the present invention, the wet process sulfur process system preferably further includes a feedwater preheater, and the boiler is given
The gas inlet end of water preheater is connect with the bottom hot air outlet of the sulfuric acid vapor condenser, for recycling sulfuric acid vapor
The heat of condenser cold side hot-air.Hot air temperature is down to 120~150 DEG C.Boiler feed temperature after preheating obtains
To promotion, thus can the more steam of output, improve the heat utilization ratio of device.
Hot-air is two parts by hot-air using the measure utilized is shunted by this preferred embodiment, and a part enters pot
Furnace feed water preheater, another part are fed directly to H2S burner.Into H2This part hot-air of S burner finally with
It is discharged lower than hot-air by the temperature of feedwater preheater.It is thus possible to improve the waste heat of hot-air recycles ability.
In the present invention, preferably, the liquid outlet of the acid mist eliminator is also connect with the sulfuric acid blending tank.
Wherein, the exhaust fan is preferably also connect with an exhaust emissions cylinder, and the exhaust emissions cylinder can be by tail gas
It is directly discharged to atmosphere.
The present invention also provides a kind of methods of secondary pressurized production concentrated sulfuric acid, use secondary pressurized as described above raw
The wet process sulfur process system for producing the concentrated sulfuric acid carries out comprising following steps: first by H2The burning of S sour gas generates SO2Process gas,
Again by SO2Process gas catalysis oxidation generates SO3Then process gas enters sulfuric acid vapor condenser with negative pressure state, is condensed into sulfuric acid
?；H2H in S sour gas2The concentration of S is >=0.5%mol, and the molar concentration is H2The mole of S accounts for H2S sour gas rubs
The percentage of your amount；The combustion air fan is used to the hot-air that the bottom of the sulfuric acid vapor condenser is discharged being forced into 15
The H is delivered to after~20kPaG2S burner；The exhaust fan after tail gas is forced into atmospheric pressure for being discharged.
Wherein, the standard value of the atmospheric pressure is generally 101.325kPa, but actual value and local height above sea level and meteorological item
Part is related.
Mechanism of the invention is: utilizing H2S sour gas is burned, by H2S is converted to SO2, then lowered temperature reclamation heat
After send into combination type reactor.SO2It is converted into gaseous state SO under the effect of the catalyst3.Then gaseous state SO3It send to special sulphur
The liquid concentrated sulfuric acid is directly condensed into acid vapor condenser. SO2Catalytic oxidation process be an exothermic reaction, subsequent reactions
The heat of generation overheats steam.
Technological operation range of the invention is wide, while being suitable for coal chemical industry high concentration and low concentration H2S operating condition, receive down to
The H of 0.5%mol concentration2S sour gas (preferably 1%mol or more), in addition in low concentration (4%-15%mol) H2Under S operating condition
Also it can stablize burning, and burning cannot be stablized in traditional wet process sulfur process under low concentration operating condition, this technique overcomes low dense
The problem of degree cannot stablize burning, meanwhile, the sour gas of high concentration (such as 20-30%mol) can also stablize combustion in burner
It burns, such as in a better embodiment of the invention, H in sour gas2S content is 29.16%mol.It should be noted that when acid
H in property gas2It when the concentration of S is less than 0.5%mol, is just stripped of, and can be directly discharged to big without this technique
Gas.
For unstripped gas source, technique of the invention can handle various sulfurous gas, may come from low-temp methanol
It washes, the sour gas of hot recycling, water-gas expansion gas, stripping acid gas, phenol recycling sour gas etc., and various forms of sulfide
Multi-stage oxidizing is carried out, the concentrated sulfuric acid of commerical grade is finally recycled into.That is, the H2S sour gas can be common for chemical field
Containing H2The acid waste gas of S.Because being wet process acid-making process, to the moisture content in unstripped gas also without too big requirement, that is,
The quite high process gas of moisture content can be received by saying.
In addition, the requirement of technique of the invention to processing flow and operating flexibility is also very wide in range, such as in certain specific implementation
In mode, the H2The flow of S sour gas is 2000Nm3/h.Technological operation elasticity is big, such as can accomplish 30%-110%'s
Operating flexibility is subjected to minimum 10% load operation lower limit (load here is for raw gas flow), adapts to flow of feed gas
The wide fluctuations of amount and sulfide concentration.
In the present invention, the pressure control before process gas to be entered to sulfuric acid vapor condenser is in negative pressure, such as control is -1.0
~0kPaG is more appropriate.The risk that process gas is leaked to environment after long period of operation not only can be avoided, use can also be reduced
In the wind pressure for giving sulfuric acid vapor condenser cold side, reduce the pressure of hot-air emptying to achieve the purpose that save power consumption.
In technique of the invention, sour gas burning zone is described below:
H in sour gas2S is combustible, and flash-point is 600 DEG C, when temperature and acid gas concentration reach certain numerical value, H2S can be with
Oxygen reaction in air, and stable hot combustion reaction is kept, it reacts as follows:
The combustion velocity is fast, H in the short time2S can be completely converted into SO2, while releasing heat.
If sour gas further includes micro CH3OH and hydrocarbons (CnHm), following react will occur simultaneously:
CnHm+(n+m/4)O2→m/2H2O+nCO2+ reaction heat (3)
Combustion reaction temperature is decided by H in sour gas2S concentration, CnHmConcentration and burning air distribution ratio.
Preferably, the H at battery limit (BL)2S sour gas is sent to H2S burner exchanges heat with by sulfuric acid vapor condenser
Hot-air afterwards is after burner premixes in H2Burning thermal response occurs in S burner, specific reaction includes above-mentioned reaction equation
(1)~(3).
Wherein, H2The ignition temperature of S sour gas is generally 800~1200 DEG C, preferably 880~1100 DEG C, the temperature
Depending on H in sour gas2S concentration, the split ratio with air quantity and hot-air of burning.
Wherein, what is produced from the bottom of the sulfuric acid vapor condenser is used for H2The temperature of the combustion air of S burner
Generally 180~230 DEG C.Generally part produces, and extraction ratio can be according to H2The burning of S sour gas it needs to be determined that.
Using primary pressurization, it is big to be generally forced into required pressure by conventional wet relieving haperacidity for 180~230 DEG C of combustion air
About 20~30kPaG.Present invention setting is pressurizeed twice, 180~230 DEG C of combustion air is forced into 15~20kPaG first, most
Secondary pressurized is used in the outlet of tail gas desulfurization scrubbing tower again afterwards, is emptied after 35~60 DEG C of tail gas is boosted to atmospheric pressure.Although
It always boosts after primary pressurization and secondary pressurized identical, but the gas temperature of secondary pressurized is low, compression efficiency is high so blower energy
It consumes lower.
Technique of the invention, than control, controls H without accurate using loose sulphur oxygen2S/O2Ratio, it is easy to operate.Wherein,
Preferably, H2H in S sour gas2S uses oxygen-excess combustion, and combustion air proportional quantity is preferably stoichiometric 1.2~2.2 times,
It is more preferably 2.1 times, that is, H2Concept (the H of S burning air distribution ratio2S/ air), air distribution is than referring to the air being added in sour gas
Mole and pure H2The ratio between mole of S.Oxygen-excess combustion may advantageously facilitate the abundant reaction of various impurity in sour gas
(hydrocarbon, alcohol, ammonia, hydrogen cyanide etc.), and these impurity often will cause device fluctuation of service problem and deterioration in quality
Problem.
In the present invention, preferably, H2S sour gas is in H2Reaction time >=1.5s in S burner.
In technique of the invention, SO2Catalytic conversion stage is described below:
In above-mentioned combustion reaction, by H2The SO that S burns2It is catalytically conveted to SO3, reaction (4) is chemical equilibrium reaction,
In view of factors such as reaction rate and equilibrium conversions, step reaction classification is carried out, it is at different levels between pass through intersegmental cooler shifting
Reaction heat out reduces the reaction temperature of process gas, and reaction equilibrium conversion is improved while taking into account reaction speed.
Wherein, preferably, when being additionally provided with a waste heat boiler between combustion furnace and combination type reactor, through the waste heat boiler
Furnace process gas temperature after cooling is generally 410 DEG C~430 DEG C, such as 420 DEG C.In addition, the introducing of waste heat boiler, and burning
The connection type of furnace and waste heat boiler can make the heat loss of combustion furnace reduce 0.2Gcal/h or more slightly lower.
When the inside of the combination type reactor is equipped with 3 catalyst beds and 2 sect heat-exchangers, exchange heat between described section
When device is sequentially distributed between the two neighboring catalyst bed, preferably, the process gas of first catalyst bed into
Mouth temperature control is at 380 DEG C or more；The process gas inlet temperature of second catalyst bed is controlled at 410 DEG C or less；It is described
The process gas inlet temperature of third catalyst bed is controlled at 390 DEG C or less.
In a better embodiment of the invention, heat technologic gas enters the first of combination type reactor with 420 DEG C from top
Catalyst bed, temperature is improved to 510 DEG C after reaction, after in the first sect heat-exchanger by being exchanged with device institute producing steam heat
After be cooled to 410 DEG C, be sent into the second catalyst bed of reactor, temperature rises to 418 DEG C after reaction, after in the second sect heat-exchanger
By being down to 385 DEG C after exchanging with device institute producing steam heat, reactor third catalyst bed is finally entered, it is final after reaction
Gas temperature is about 381 DEG C, is cooled to 280 DEG C through technique Gas Cooler, the sulfuric acid vapor condenser being sent into downstream process.
The process gas temperature for leaving technique Gas Cooler is higher than dew-point temperature, to prevent the sulfuric acid vapor condensation deposition in downstream process from making
Forming apparatus corrosion, while being conducive to protect downstream sulfuric acid vapor condenser inner coating, while protecting quartz glass heat exchanger tube, it reduces
To the thermal shock strength of coating material and quartz glass heat exchanger tube.
In the present invention, tail gas washing tower is preferably provided two sections of cyclic absorptions, and top is recycled using water, and lower part uses SO2
Absorbent circulation.The water circulation that top uses is mainly used for sulfate liquor or the sulfuric acid acid for removing lower part by entrainment
Mist.Lower part mainly utilizes SO2Absorbent is to tail gas SO2It is removed
In technique of the invention, SO3Conversion and H2SO4Steam condensation is described below:
H2H caused by S combustion reaction (reaction 1)2The SO that O will be obtained with catalyzed conversion3Following reaction occurs:
SO3(g)+H2O(g)→H2SO4(g)+reaction heat (5)
Then sulfuric acid vapor will cool down condensation in sulfuric acid vapor condenser, while release reaction heat:
H2SO4(g)→H2SO4(L)+reaction heat (6)
In the present invention, SO3Water content is preferably 9.96% in process gas.In the present invention, SO3Process gas enters sulfuric acid steaming
The inlet temperature of vapour condenser is preferably 285~295 DEG C, is more preferably 290~295 DEG C.
In the present invention, the outlet hot blast temperature of sulfuric acid vapor condenser is preferably maintained at 180 DEG C or so.Export hot wind temperature
Degree is higher, and cooling air quantity is smaller, can reduce the load of air-cooler, more be conducive to the energy-saving of device.If but outlet temperature
The too high temperature allowed more than top cover anticorrosive paint and other equipment, it will damage equipment loses more than gain.
In a better embodiment of the invention, SO3Process gas enters sulfuric acid vapor condenser, into one in the condenser
Step reduces temperature, and sulfuric acid vapor is promoted to be condensed into sulfuric acid.SO3Process gas enters sulfuric acid vapor condenser, from bottom to top along shell side
Flowing.The air being sent into tube side exchanges heat as cold medium and thermal process gas and reduces the temperature of thermal process gas to 93 DEG C,
Reduced with thermal process temperature degree, sulfuric acid vapor is gradually condensed on glass heat exchange pipe, after form drop, be dropped in sulphur by gravity
The bottom of acid vapor condenser.Air after primary air fan pressure-raising by sending to sulfuric acid vapor condenser, into the top of bobbin carriage, bobbin carriage
Divide left and right ends, multistage is divided by internal partition respectively, air enters the transverse direction of the partition after air bobbin carriage inside bobbin carriage
Into glass heat exchange pipe, glass tube is washed away, is exchanged with thermal process gas heat, out other the one of air bobbin carriage after glass heat exchange pipe
End is collected, and next section in bobbin carriage is then proceeded to, and forms S type stream by this method, exchanges heat with Process Gas cross-flow, eventually off
The air themperature of sulfuric acid vapor condenser is about 180 DEG C.The sulfuric acid temperature that sulfuric acid vapor condenser bottom is sent out is about 252 DEG C.
In the present invention, preferably, the outlet exhaust temperature of the sulfuric acid vapor condenser is controlled at 93 DEG C or less；Air with
Tail gas pressure difference is controlled in 3Kpa.
In the present invention, the concentrated sulfuric acid temperature generated by sulfuric acid vapor condensation is higher, preferably, also taking cold sulfuric acid mixing anxious
Cold and heat exchange is cooled to 40 DEG C, sends out battery limit (BL) afterwards.
Under the high temperature conditions, part SO3Hydration reaction is generated into H2SO4Steam is reduced with temperature, the degree of hydration reaction
It will move to right, reaction refers to above-mentioned reaction equation (5) and reaction equation (6).
Above reaction (1)~(6) are exothermic reaction, and device produces saturated vapor within battery limit using outer boiler of feeding water,
And the mode of follow-up steam overheat removes the reaction heat of each section of reaction, holding meanss thermal balance, while by-product high-quality steam.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: the wet process sulfur process of the secondary pressurized production concentrated sulfuric acid provided by the invention
System and method, wherein after single-stage combustion, H2H in S sour gas2S total conversion is up to 99.9% or more；Catalytic oxidation process
In, SO2Conversion ratio is 99.5% or more.In general, the sulfur recovery rate of technique is up to 99.8%, SO2Exhaust emissions concentration is
100mg/Nm3Hereinafter, requiring to be less than 400mg/Nm far below country GB16297-20133New standard；The sulfuric acid product of production
Concentration can reach 97-98wt%, free from foreign meter, and coloration is as clear as crystal, and quality reaches national GB534-2014 high-class product standard.
The present invention improves the convenience of operation, the stability of equipment and the use tolerance and concentration range of sour gas.
The present invention compares WSA technology, and technological operation is simple, and equipment is stablized, and invests lower；Compared to cryogenic condensation technique and Kang Kai secret service
Skill, the use concentration range of unstripped gas does not limit, and can handle the H of low concentration and high concentration simultaneously2S sour gas receives low
To the H of 0.5%mol concentration2S acid gas.
In addition the device of the invention autothermal equilibrium is without the use of pure oxygen without outer heating load, also without fuel gas consumption and tail
Gas degree of purification is high, being capable of qualified discharge.
Technique provided by the invention is bigger compared to more traditional wet process sulfur process superheated steam yield (to provide 10% left side
It is right), energy consumption it is lower (10%~30% or so can be reduced).
The present invention is by H2The conversion of S acid waste gas is produced as dense H2SO4Method, overcome existing wet process legal system technic acid
Energy consumption it is high, easily leakage the problem of.Can achieve higher desulfuration efficiency, process flow is simple, and low energy consumption, and it is without secondary pollution,
Simultaneously can by-product high-grade middle pressure steam and be able to achieve higher economic benefit.
Detailed description of the invention
Fig. 1 is the process flow chart that the secondary pressurized of the embodiment of the present invention 1 produces the wet process sulfur process system of the concentrated sulfuric acid.
Fig. 2 is the structural schematic diagram of the sulfuric acid vapor condenser of the embodiment of the present invention 1.
In Fig. 1, the reference numerals are as follows:
Sulfuric acid vapor condenser 1
Combustion furnace 4
Waste heat boiler 401
Combination type reactor 5
First catalyst bed 501
First sect heat-exchanger 502
Second catalyst bed 503
Second sect heat-exchanger 504
Third catalyst bed 505
Technique Gas Cooler 506
Acid mist eliminator 6
Sulfuric acid blending tank 7
Tail gas washing tower 8
Electrostatic precipitator 801
Exhaust fan 802
Exhaust emissions cylinder 803
Cooling blower 901
Combustion air fan 902
Middle pressure drum 10
Feedwater preheater 101
In Fig. 2, the reference numerals are as follows:
Sulfuric acid vapor condenser 1
Exhaust port 11
Air inlet 12
Leakage fluid dram 13
Glass tube 21
Glass tube 22
U-shaped band tubing 23
Fiber filter plate 3
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
The wet process sulfur process system of the secondary pressurized production concentrated sulfuric acid provided in this embodiment is as shown in Figure 1, described secondary
The wet process sulfur process system of the pressurization production concentrated sulfuric acid includes the combination type reactor that a combustion furnace 4, one is connected with combustion furnace 4
5, a sulfuric acid vapor condenser 1 (as shown in Figure 2), an acid mist eliminator 6 and a tail gas washing tower 8.
Combustion furnace 4, which is used to burn hydrogen sulfide sour gas, generates SO2Process gas, combination type reactor 5 are used for SO2Technique
Gas catalysis oxidation generates SO3Process gas.
Combustion furnace 4 has a burner, and there is burner a central passage and ring to be located at the circular passage outside central passage, in
Heart channel is for being passed through H2The mixed gas of S sour gas and air, circular passage is for being passed through fuel gas.Using sour gas cofiring
Technology, the i.e. burner of special designing, sour gas and air burning are sent into hole pulse in its center, while fuel gas passes through burner ring
It is aftercombustion, improves the stability of sour gas burning, which solves H in sour gas2S fluctuation of concentration is big, ensures
Low concentration (4%- 15%mol) H2Stablize reaction under S operating condition.Burner Load Regulation speed is fast, adaptable, gasification effect
Rate is high.
Wherein, waste heat boiler 401 of the combustion furnace 4 also with a downstream is directly connected to, the gas vent of waste heat boiler 401 also with
The top of combination type reactor 5 connects.Heat technologic gas after burning is directly entered entering for waste heat boiler 401 by combustion furnace 4
Mouth tube side, enters combination type reactor 5 from top after cooling down.Combustion furnace 4 is directly connected to downstream waste heat boiler 401, is used
Direct heat transfer technology, heat recovery efficiency is high, overcomes the defect of equipment easy fouling and blocking.
Wherein, the heat transferring medium exit of waste heat boiler 401 also presses drum 10 to connect with one, outlet setting steam superheating
Device.
In the present embodiment, the inside of combination type reactor 5 is equipped with 3 catalyst beds and 2 sect heat-exchangers: respectively
It is denoted as the first catalyst bed 501, the second catalyst bed 503 and third catalyst bed 505, sect heat-exchanger is sequentially distributed
Between two neighboring catalyst bed, it is denoted as the first sect heat-exchanger 502, the second sect heat-exchanger 504 respectively.First catalysis
It is filled with catalyst in agent bed 501, the second catalyst bed 503 and third catalyst bed 505, the top of bed sets people
Hole, lower part set catalyst discharge port.Under the action of catalyst, SO2Catalysis oxidation is converted into SO3, combustion reaction section is excessive combustion-supporting
Air helps to improve SO2Reaction equilibrium conversion.The combination type reactor 5 is compact-sized, save the cost, optimizes space cloth
It sets, convenient for manufacture maintenance, and is conducive to the recycling of thermal energy gradient, it is scientific and reasonable.
First sect heat-exchanger 502,504 bottom of the second sect heat-exchanger and housing parts are fixed using steel channel beam；
Top and housing parts are attached using conical shell, and connection type guarantees the first sect heat-exchanger 502, the using being slidably connected
The free extension of two sect heat-exchangers 504；What the first sect heat-exchanger 502, the second sect heat-exchanger 504 were connected with shell connects
Pipe should have enough length, keep certain flexibility, prevent from generating shell excessive local stress.
Wherein, process gas is entered by the entrance on 5 top of combination type reactor, into the first catalyst bed 501.Gas
After the first catalyst bed 501, Partial Conversion is completed, the hot gas after reaction passes through the flase floor of bed lower part.Grid
The double-deck silk screen of 10*10mm- string diameter Φ 2mm, 25 millimeters of porcelain balls of Φ of H=75mm, 3*3mm- string diameter Φ are successively laid with above plate
The double-deck silk screen of 1mm, prevents catalyst breakage from falling into next sheaf space.Process gas passes through flase floor, enters first by conical shell
Sect heat-exchanger 502；First sect heat-exchanger 502 and the second sect heat-exchanger 504 use coiled pipe structure, and centre uses three pieces
Support plate support, to guarantee free extension, heat exchanger tube does not weld with support plate, keeps being slidably connected；With stainless outside heat exchanger tube
Steel plate sealing, prevents process gas from passing through the gap between heat exchanger tube and support plate.And so on, process gas passes sequentially through second and urges
Agent bed 503, the second sect heat-exchanger 504, after third catalyst bed 505, the bottom of combination type reactor 5 is additionally provided with one
Technique Gas Cooler 506, process gas is after technique Gas Cooler 506 is cooling, then from the lower outlet stream of combination type reactor 5
Out.
Sulfuric acid vapor condenser 1 is used for SO3Process gas condenses to form sulfuric acid；Acid mist eliminator 6 and sulfuric acid vapor condense
Device 1 connects, and junction is located between the air inlet 12 and exhaust port 11 of sulfuric acid vapor condenser 1, for trapping abjection folder
The sulfuric acid aerosol of band.
As shown in Fig. 2, the sulfuric acid vapor condenser 1 in the present embodiment includes a rectangular shell placed vertically, it should
The top of shell has an exhaust port 11, has an input SO in the bottom of shell3The air inlet 12 of process gas.?
The lower section of air inlet 12 also has a leakage fluid dram 13, for the condensed concentrated sulfuric acid to be discharged.Wherein, the bottom of the shell is at half
Circular configuration, leakage fluid dram 13 are located at the bottom of semicircular structure.Certainly, housing bottom can be other along liquid discharge direction
Diminishing structure, such as up-side down triangle or inverted trapezoidal.In addition, the upstream that the top of shell is located at exhaust port 11 is set
There is a fiber filter plate 3 as filter mechanism, for filtering the liquid little particle in the tail gas generated after condensation.
12 glass are vertically equipped with along long axis direction (i.e. vertical direction in Fig. 2) between shell arranged on left and right sides wall
Pipe, the both ends of all glass tubes all extend to the outside of shell.It is adjacent between the upstream and downstream of the flow direction of cold air
Two glass tubes, i.e. successively first (end) tail (end) is connected for upper and lower two adjacent glass tubes in Fig. 2, so that formation one is from upper
Under and, the cold air flow passage of one-way guide flow.In the present embodiment, two adjacent glass tubes are connected to by a U-shaped band tubing 23.
The cold air flow passage includes that an inlet of cold air for being located at upper part of the housing and a cold air positioned at lower part of the housing go out
Mouthful, air enters after cooling blower 901 is cooling from inlet of cold air, flows to cold-air vent along cold air flow passage and is arranged
Out.In the present embodiment, which is the head end of glass tube 21, and cold-air vent is the tail end of glass tube 22.Sulfuric acid steams
The bottom of vapour condenser 1 also passes through a combustion air fan 902 and is connected with combustion furnace 4, and combustion air fan 902 is for condensing sulfuric acid vapor
Combustion furnace 4 is delivered to after the hot-air pressurization of the bottom discharge of device 1.
In sulfuric acid vapor condenser 1 described in the present embodiment, by the cold air channel energy for the one-way guide flow that glass tube is formed
It is enough resistant to high temperature and deep-etching, avoids occurrence of equipment deformation and corrosion damage phenomenon in high temperature and severe corrosive environment, it is ensured that
Condenser uses for a long time, improves the safety in utilization and fluency of sulfuric acid vapor condenser 1.
In the present embodiment, acid mist eliminator 6 is a high-speed fibre demister.It is trapped by high-efficiency fiber demister physics
Method realizes that demisting efficiency >=95%, pressure drop is small (≤1.0KPa), does not influence exhaust emissions to the efficient process of acid mist.It is high
Fast fiber mist eliminator is woven to layered filter using the filter screen of high-intensitive fibre cleavages silk package PTFE, when containing sulphur
When the process gas of acid droplet (acid mist) passes through the filter, intercepted by forcing, the sulfuric acid gas that realization is carried secretly to acid mist and wherein
The efficient trapping of colloidal sol, then tail gas drains into chimney emptying, and filtering accuracy is up to 99.99% (>=0.5um).
Wherein, it (is introduced technology instead of foreign countries by the interior fiber filter plate 3 set and external high-speed fibre demister cooperation
The purpose of operation of the combusting silicone oil manufacture nuclei of condensation, the operation is enhancing sulfuric acid vapor condensation, and it is dense to reduce sulfuric acid aerosol in tail gas
Degree), the sulfuric acid mist carried secretly in gas is removed, higher sulfuric acid mist capture rate is can achieve, is substantially free of in emptying end gas
Acid mist also can guarantee acid mist qualified discharge in tail gas even if there is micro acid mist (≤10ppm).
The top of acid mist eliminator 6 is also connect with tail gas washing tower 8, and the top gas outlet of tail gas washing tower 8 is also successively
Equipped with an electrostatic precipitator 801 and an exhaust fan 802, exhaust fan 802 after tail gas pressurizes for being discharged.
In the present embodiment, the leakage fluid dram 13 of sulfuric acid vapor condenser 1 is also connect with a sulfuric acid blending tank 7.
It should be noted that when the shell of sulfuric acid vapor condenser 1 is a cylindrical body, the axis extension side of the cylindrical body
To the long axis direction of as shell, and it is the side wall that cylindrical body, which is formed by surface then around axis convolution,.
In addition, the head end and tail end of glass tube can be respectively positioned on enclosure interior, the initial and end of the glass tube passes through adaptation at this time
Glass pipe connection.It with no restrictions to the shape for being formed by cold air flow passage at this, can be " bow " font, " Z " word
Type or other shapes.
Wherein, cold air is cold air, and the flow direction design for the characteristic of cooperation cold air decline, upper entering and lower leaving can be further
The mobility of cold air is improved, velocity of medium is improved, then improves condensation efficiency.
Wet process sulfur process system further includes a feedwater preheater 101, the gas of feedwater preheater 101 into
Mouth end is connect with the bottom hot air outlet of sulfuric acid vapor condenser 1, for recycling 1 cold side hot-air of sulfuric acid vapor condenser
Heat.Hot air temperature is down to 120~150 DEG C.Boiler feed temperature after preheating gets a promotion, therefore energy output is more
More steam improves the heat utilization ratio of device.
In the present embodiment, the liquid outlet of acid mist eliminator 6 is also connect with sulfuric acid blending tank 7.
Wherein, exhaust fan 802 is also connect with an exhaust emissions cylinder 803, and exhaust emissions cylinder 803 can directly arrange tail gas
It puts to atmosphere.
Correspondingly, the acid-making process in the present embodiment includes the following steps:
(1) sour gas burns
180~230 DEG C of combustion air is forced into 15kPaG, carries out sour gas burning, combustion furnace 4 is fired using second level
It burns, i.e., swirl flow device is set in burner hearth, be equivalent to the secondary Forced Mixing of setting, combustion intensity can be greatly improved.Combustion furnace 4
In, process gas operation temperature is between 880~1100 DEG C.
(2) process gas catalysis oxidation
Process gas after burning makes SO using multi-stage oxidizing2Process gas catalysis oxidation generates SO3。SO2Overall conversion
It can reach 99~99.5%.
(3) sulfuric acid vapor condenses
SO3Enter sulfuric acid vapor condenser 1, the one-way guide flow formed by glass tube with negative pressure state (- 1.0~0kPaG)
Cold air channel be resistant to high temperature and deep-etching, avoid in high temperature and severe corrosive environment occurrence of equipment deformation and corrosion
Damage phenomenon, it is ensured that 1 long-time of sulfuric acid vapor condenser uses, and improves the safety in utilization and stream of sulfuric acid vapor condenser 1
Smooth property.
Combustion air fan 902 is used to the part hot-air that the bottom of sulfuric acid vapor condenser 1 is discharged being forced into 15kPaG
Afterwards, then and from out-of-bounds containing H2The burner entrance that S sour gas is sent into combustion furnace 4 together is mixed and burned；Exhaust fan
802 after tail gas is forced into atmospheric pressure for being discharged.
(4) control of acid fog
Control of acid fog forces interception mode using Multi-stage precise, directly controls outlet acid mist≤10ppm.
(5) tail gas zero-emission
In the present embodiment, the offgas outlet of acid mist eliminator 6 also connects with a tail gas washing tower 8, and H is arranged in tail gas2O2Potent oxygen
Change unit, SO in device exhaust2≤ 70mg/Nm can be reduced to3, both SO of trace2Pass through H2O2The washing of weak solution, by H2O2Directly
It connects and is oxidized to SO3, sulfuric acid droplets are formed, and then collect by acid mist eliminator, and condense and obtain 60%wt sulfuric acid, are incorporated to sulfuric acid
In product, the minimum discharge of tail gas, tail gas SO are so realized2Can≤50mg/Nm3, realize minimum discharge, current industry can be met
Technology expectation to the zero-emission of environmental protection.
In the present embodiment, with flow 2000Nm3/ h, H2S:29.16mol% is acid gas data, and device can be handled
H2It 20.4 ton/days of S equivalent, can produce 63 ton/days of equivalent of sulfuric acid (98wt%), 125.7 tons of superheated steam (420 DEG C, 4.0MPa).
In step (1), the ignition temperature of sour gas is 903.7 DEG C.Combustion air proportional quantity is 2.1 times. H2S sour gas
Reaction time 1.5s in combustion furnace.It is 420 DEG C through the process gas temperature after cooling of waste heat boiler 401.
In step (2), heat technologic gas enters the first catalyst bed 501 of combination type reactor 5 with 420 DEG C from top,
Temperature is improved to 510 DEG C after reaction, after in the first sect heat-exchanger 502 by being cooled to after being exchanged with device institute producing steam heat
410 DEG C, be sent into the second catalyst bed of reactor 503, temperature rises to 418 DEG C after reaction, after it is logical in the second sect heat-exchanger 504
It crosses after being exchanged with device institute producing steam heat and is down to 385 DEG C, finally enter reactor third catalyst bed 505, after reaction most
Whole gas temperature is about 381 DEG C, is cooled to 280 DEG C through technique Gas Cooler 506, the sulfuric acid vapor condensation being sent into downstream process
Device 1.
In the present embodiment, from the SO of step (2) discharge3Water content is 9.96% in process gas.SO3Process gas enters sulfuric acid
The inlet temperature of steam condenser 1 is 275~295 DEG C.In the present embodiment, the outlet hot blast temperature of sulfuric acid vapor condenser 1 is protected
It holds at 180 DEG C or so.
SO3Process gas enters sulfuric acid vapor condenser 1, further decreases temperature, and sulfuric acid vapor is promoted to be condensed into sulfuric acid.SO3
Process gas enters sulfuric acid vapor condenser 1, flows from bottom to top along shell side.The air being sent into tube side is as cold medium and hot mistake
Journey gas exchange heat and reduce the temperature of thermal process gas to 93 DEG C, reduced with thermal process temperature degree, sulfuric acid vapor gradually condenses
In on glass heat exchange pipe, after form drop, the bottom of sulfuric acid vapor condenser 1 is dropped in by gravity.Air is mentioned by primary air fan
It is sent after pressure to sulfuric acid vapor condenser 1, into the top of bobbin carriage, bobbin carriage divides left and right ends, is divided into respectively by internal partition
Multistage, the partition that air enters after air bobbin carriage inside bobbin carriage enter laterally glass heat exchange pipe, wash away glass tube, with thermal process
The exchange of gas heat, the other end after glass heat exchange pipe in air bobbin carriage is collected out, then proceedes to next section in bobbin carriage,
S type stream is formed by this method, is exchanged heat with Process Gas cross-flow, the air themperature of eventually off sulfuric acid vapor condenser 1 is about 180
℃.The sulfuric acid temperature that 1 bottom of sulfuric acid vapor condenser is sent out is about 252 DEG C.
In the present embodiment, the outlet exhaust temperature of sulfuric acid vapor condenser 1 is controlled at 93 DEG C or less；Air and tail gas pressure difference
Control is in 3Kpa.
In the present embodiment, by sulfuric acid vapor condensation generate concentrated sulfuric acid temperature it is higher, also take cold sulfuric acid mixing chilling with
And heat exchange is cooled to 40 DEG C, sends out battery limit (BL) afterwards.
In the present embodiment, the hot-air of sulfuric acid vapor condenser 1 is sent out, partially pressure is improved through secondary air fan, send to dress
The combustion furnace 4 of leading portion is set as combustion air, remaining air send chimney to be vented, to improve the temperature and lift of emptying end gas.
When normal operating, device exhaust emission behaviour is as follows:
SO2: 80mg/Nm3(design requirement: < 100)
SO2Rate of discharge: 8.5kg/h
H2S concentration: it can not detect
H2S mass rate of emission: it can not detect
COS+CS2Concentration: it can not detect
COS+CS2Mass rate of emission: it can not detect
SO3Concentration: 26mg/Nm3(design requirement: < 45)
SO3Mass rate of emission :≤2.1kg/h
NOxConcentration: 80mg/Nm3(design requirement: < 240)
NOxMass rate of emission: 1.8kg/h
Waste water: nothing
Waste residue and waste liquid: nothing
Embodiment 2
Process flow chart, the sulfuric acid vapor of the wet process sulfur process system of the secondary pressurized production concentrated sulfuric acid of the present embodiment are cold
Condenser is as shown in Fig. 1~2, in the present embodiment, with flow 34328Nm3/ h, H2S concentration: 1%mol is acid gas, can be produced
142 ton/days of equivalent of sulfuric acid (93wt%), 350.4 ton/days of superheated steam (420 DEG C, 4.0MPa).
In step (1), the ignition temperature of sour gas is 896 DEG C.Combustion air proportional quantity is 2.1 times. H2S sour gas exists
Reaction time 1.5s in combustion furnace.It is 420 DEG C through the process gas temperature after cooling of waste heat boiler 401.
In step (2), heat technologic gas enters the first catalyst bed 501 of combination type reactor 5 with 420 DEG C from top,
Temperature is improved to 510 DEG C after reaction, after in the first sect heat-exchanger 502 by being cooled to after being exchanged with device institute producing steam heat
410 DEG C, be sent into the second catalyst bed of reactor 503, temperature rises to 418 DEG C after reaction, after it is logical in the second sect heat-exchanger 504
It crosses after being exchanged with device institute producing steam heat and is down to 385 DEG C, finally enter reactor third catalyst bed 505, after reaction most
Whole gas temperature is about 381 DEG C, is cooled to 280 DEG C through technique Gas Cooler 506, the sulfuric acid vapor condensation being sent into downstream process
Device 1.
In the present embodiment, from the SO of step (2) discharge3Water content is 9.96% in process gas.SO3Process gas enters sulfuric acid
The inlet temperature of steam condenser 1 is 290~295 DEG C.In the present embodiment, the outlet hot blast temperature of sulfuric acid vapor condenser 1 is protected
It holds at 180 DEG C or so.
SO3Process gas enters sulfuric acid vapor condenser 1, further decreases temperature, and sulfuric acid vapor is promoted to be condensed into sulfuric acid.SO3
Process gas enters sulfuric acid vapor condenser 1, flows from bottom to top along shell side.The air being sent into tube side is as cold medium and hot mistake
Journey gas exchange heat and reduce the temperature of thermal process gas to 93 DEG C, reduced with thermal process temperature degree, sulfuric acid vapor gradually condenses
In on glass heat exchange pipe, after form drop, the bottom of sulfuric acid vapor condenser 1 is dropped in by gravity.Air is mentioned by primary air fan
It is sent after pressure to sulfuric acid vapor condenser 1, into the top of bobbin carriage, bobbin carriage divides left and right ends, is divided into respectively by internal partition
Multistage, the partition that air enters after air bobbin carriage inside bobbin carriage enter laterally glass heat exchange pipe, wash away glass tube, with thermal process
The exchange of gas heat, the other end after glass heat exchange pipe in air bobbin carriage is collected out, then proceedes to next section in bobbin carriage,
S type stream is formed by this method, is exchanged heat with Process Gas cross-flow, the air themperature of eventually off sulfuric acid vapor condenser 1 is about 180
℃.The sulfuric acid temperature that 1 bottom of sulfuric acid vapor condenser is sent out is about 252 DEG C.
In the present embodiment, the outlet exhaust temperature of sulfuric acid vapor condenser 1 is controlled at 93 DEG C or less；Air and tail gas pressure difference
Control is in 3Kpa.
In the present embodiment, by sulfuric acid vapor condensation generate concentrated sulfuric acid temperature it is higher, also take cold sulfuric acid mixing chilling with
And heat exchange is cooled to 40 DEG C, sends out battery limit (BL) afterwards.
In the present embodiment, the hot-air of sulfuric acid vapor condenser 1 is sent out, partially pressure is improved through secondary air fan, send to dress
The combustion furnace of leading portion is set as combustion air, remaining air send chimney to be vented, to improve the temperature and lift of emptying end gas.
When normal operating, device exhaust emission behaviour is as follows:
SO2: 50mg/Nm3(design requirement: < 100)
H2S concentration: it can not detect
H2S mass rate of emission: it can not detect
COS+CS2Concentration: it can not detect
COS+CS2Mass rate of emission: it can not detect
SO3Concentration: 5mg/Nm3(design requirement: < 5)
NOxConcentration: 80mg/Nm3(design requirement: < 240)
Waste water: nothing
Waste residue and waste liquid: nothing.
Claims (10)
1. a kind of wet process sulfur process system of the secondary pressurized production concentrated sulfuric acid, which is characterized in that wet process sulfur process system
System includes a H2S burner, one and the H2The connected combination type reactor of S burner, a sulfuric acid vapor condenser, one
Acid mist eliminator and a tail gas washing tower；
The H2S burner, which is used to burn hydrogen sulfide sour gas, generates SO2Process gas, the combination type reactor is used for will
SO2Process gas catalysis oxidation generates SO3Process gas, the inside of the combination type reactor are equipped with several catalyst beds and divide
The sect heat-exchanger being distributed between the two neighboring catalyst bed；
The sulfuric acid vapor condenser is used for SO3Process gas condenses to form sulfuric acid, and the sulfuric acid vapor condenser includes a shell
The top of body, the shell is equipped with an exhaust port, has an input SO in the bottom of the shell3The air inlet of process gas
Mouthful, it is additionally provided with a leakage fluid dram below the air inlet, is equipped with and is used for along the long axis direction of the shell in the shell
If the stem glass tube for the cold air that circulates, the glass tube are located between the two sidewalls of the shell, the glass tube is located at
One end of the cold air upstream is head end, and one end positioned at the cold air downstream is tail end, in the upstream and downstream of the cold air
Between the adjacent glass tube be connected to end to form the cold air flow passage of at least one one-way guide flow；The sulfuric acid steams
The bottom of vapour condenser also passes through a combustion air fan and the H2S burner is connected, and the combustion air fan is used for the sulphur
The H is delivered to after the hot-air pressurization of the bottom discharge of acid vapor condenser2S burner；
The acid mist eliminator is connect with the sulfuric acid vapor condenser, and junction is set to the air inlet and the exhaust emissions
On shell between mouthful, for trapping the sulfuric acid aerosol of abjection entrainment；
The top of the acid mist eliminator is also connect with the tail gas washing tower, and the top gas outlet of the tail gas washing tower is also
It is successively arranged an electrostatic precipitator and an exhaust fan, the exhaust fan after tail gas pressurizes for being discharged.
2. wet process sulfur process system as described in claim 1, which is characterized in that the H2S burner has a burner,
The burner has a central passage and ring is located at the circular passage outside the central passage, and the central passage is for being passed through
H2The mixed gas of S sour gas and air, the circular passage is for being passed through fuel gas.
3. wet process sulfur process system as described in claim 1, which is characterized in that the H2S burner is a combustion furnace,
Swirl flow device is provided in its burner hearth；
Waste heat boiler of the combustion furnace also with a downstream is directly connected to, the gas vent of the waste heat boiler also with described group
The top of box-like reactor connects.
4. wet process sulfur process system as described in claim 1, which is characterized in that the heat transferring medium of the waste heat boiler exports
Also drum is pressed to connect with one, steam superheater is arranged in the outlet of medium pressure drum；
The inside of the combination type reactor is equipped with 3 catalyst beds and 2 sect heat-exchangers, and the sect heat-exchanger is successively
It is distributed between the two neighboring catalyst bed, is denoted as the first catalyst bed, the first sect heat-exchanger, from top to bottom
Two catalyst beds, the second sect heat-exchanger and third catalyst bed；The bottom of the combination type reactor is additionally provided with a work
Skill Gas Cooler.
5. wet process sulfur process system as described in claim 1, which is characterized in that the top of the sulfuric acid vapor condenser is also
Equipped with a fiber filter plate；
In the sulfuric acid vapor condenser, the leakage fluid dram is also connect with a sulfuric acid blending tank；
The acid mist eliminator is a high-speed fibre demister；
The wet process sulfur process system further includes a feedwater preheater, the gas inlet end of the feedwater preheater
It is connect with the bottom hot air outlet of the sulfuric acid vapor condenser, for recycling the heat of sulfuric acid vapor condenser cold side hot-air
Amount；
The liquid outlet of the acid mist eliminator is also connect with the sulfuric acid blending tank；
Wherein, the exhaust fan is also connect with an exhaust emissions cylinder.
6. a kind of method of the secondary pressurized production concentrated sulfuric acid, which is characterized in that it is used such as Claims 1 to 5 any one institute
The wet process sulfur process system stated carries out comprising following steps: first by H2The burning of S sour gas generates SO2Process gas, then by SO2
Process gas catalysis oxidation generates SO3Then process gas enters sulfuric acid vapor condenser with negative pressure state, is condensed into sulfuric acid；
H2H in S sour gas2The concentration of S is >=0.5%mol, and the molar concentration is H2The mole of S accounts for H2The mole of S sour gas
Percentage；The combustion air fan is used to for the hot-air that the bottom of the sulfuric acid vapor condenser is discharged being forced into 15~
The H is delivered to after 20kPaG2S burner；The exhaust fan after tail gas is forced into atmospheric pressure for being discharged.
7. method as claimed in claim 6, which is characterized in that H2H in S sour gas2The concentration of S is 1%mol or more, preferably
For 4%-15%mol.
8. method as claimed in claim 6, which is characterized in that H2H in S sour gas2The concentration of S is 20-30%mol, preferably
For 29.16%mol.
9. method as claimed in claim 6, which is characterized in that will be controlled into the process gas pressure before sulfuric acid vapor condenser
In -1.0~0kPaG；
H2The ignition temperature of S sour gas is 800~1200 DEG C, preferably 880~1100 DEG C；H2The combustion process of S sour gas
In, air stoichiometry amount is stoichiometric 1.2~2.2 times, preferably 2.1 times；
H2S sour gas is in H2Reaction time >=1.5s in S burner；
What is produced from the bottom of the sulfuric acid vapor condenser is used for H2The temperature of the combustion air of S burner is 180~230
℃；The exhaust fan after 35~60 DEG C of tail gas is boosted to atmospheric pressure for emptying；
When being additionally provided with a waste heat boiler between combustion furnace and combination type reactor, through waste heat boiler SO after cooling2Technique
The temperature of gas is 410 DEG C~430 DEG C.
10. method as claimed in claim 6, which is characterized in that when the inside of the combination type reactor is equipped with 3 catalyst
Bed and 2 sect heat-exchangers, it is described when the sect heat-exchanger is sequentially distributed between the two neighboring catalyst bed
The SO of first catalyst bed2Process gas inlet temperature is controlled at 380 DEG C or more；The process gas of second catalyst bed into
Mouth temperature control is at 410 DEG C or less；The process gas inlet temperature of the third catalyst bed is controlled at 390 DEG C or less；
In the sulfuric acid vapor condenser, H is also passed through in condensation process2O2Solution is used for SO3The trace carried secretly in process gas
The SO of amount2It is oxidized to SO3, then through condensation form sulfuric acid droplets；SO3Water content is 9.96% in process gas；SO3Process gas enters
The inlet temperature of the sulfuric acid vapor condenser is 285~295 DEG C, preferably 290~295 DEG C.
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