CN109573959A - The multi-stage oxidizing sulphuric acid plant and acid-making process of hydrogen sulfide sour gas - Google Patents
The multi-stage oxidizing sulphuric acid plant and acid-making process of hydrogen sulfide sour gas Download PDFInfo
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- CN109573959A CN109573959A CN201910008441.9A CN201910008441A CN109573959A CN 109573959 A CN109573959 A CN 109573959A CN 201910008441 A CN201910008441 A CN 201910008441A CN 109573959 A CN109573959 A CN 109573959A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
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Abstract
The invention discloses a kind of multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas and acid-making process, which includes a H2S burner, one and H2S burner connected combination type reactor, a sulfuric acid vapor condenser and an acid mist eliminator；H2S burner, which is used to burn hydrogen sulfide sour gas, generates SO2Process gas, combination type reactor are used for SO2Process gas catalysis oxidation generates SO3Process gas, the sect heat-exchanger that the inside of combination type reactor is equipped with several catalyst beds and is distributed between two neighboring catalyst bed；Sulfuric acid vapor condenser is used for SO3Process gas condenses to form sulfuric acid；Acid mist eliminator is connect with sulfuric acid vapor condenser, and junction is located between the air inlet and exhaust port of sulfuric acid vapor condenser.Technique provided by the invention can handle the hydrogen sulfide sour gas of high concentration and low concentration simultaneously, and significantly reduce plant investment and operating cost.
Description
Technical field
The present invention relates to a kind of multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas and acid-making process.
Background technique
H2S is one of the most common toxicant of chemical industry and polluter, in coal chemical industry, petrochemical industry, steel smelting
In the industries such as refining, raw material (petroleum or coal) is in chemical process, conversion and extractive process, and processing is containing the related of sulfur feedstock
Enterprise can generate containing H2The sour gas of S.H2S gas is toxic, and inflammable and explosive, is unable to direct emission.And what coal gasification generated
Contain H in synthesis gas2S, after transformation and desulfurization and decarburization, H2S will give off device, the H2S sour gas must be handled strictly,
Otherwise the H being vented2S has toxicity, and it pollutes environment, leads to the long-term stench taste of plant area, influences plant area's ring of enterprise's device
Border, while H2S is oxidized to SO in air2It will cause acid rain, serious harm caused to people and ecological environment, is refined oil thus
Device or coal chemical engineering equipment must be provided with H2S processing unit.
But the H routinely used2S processing technique is mainly translated into sulphur.For high concentration H2S gas ψ ((H2S)≥
15%) Clausius equlity sulphur, is usually used, but Claus method purifying rate is low, tail gas SO2Cannot be up to standard, it needs further to locate
Reason, while Crouse's technology fluctuation of service in coal chemical engineering equipment, not only investment is high, and operating cost is high, and there is
The defect of many technical aspects, such as complex process, ingredient requirement is harsh, catalyst is easily poisoned, device continuous operating time is short.
For low concentration H2S gas, often uses wet oxidation process (tannin extract) Recovered sulphur, and wet oxidation process Recovered sulphur, long flow path,
Site environment is poor, and product sulphur is second-rate, influences market.In addition, if contain other impurities in gas, as HCN, COS,
CS2, tar, benzene etc., will affect the operation of device or reduce final sulfur recovery rate, moreover sulphur is not required for user sometimes
Product.
H is used in these cases2S gas generation sulfuric acid will be a kind of very attractive selection.Use H2S produces sulfuric acid can
Many technical process are saved, investment and production cost are reduced, make product that there is the stronger market competitiveness.It is urged according to sulfur dioxide
Change the process conditions of conversion, H2S relieving haperacidity can be divided into dry contact method and wet contact method.So-called dry contact method is by H2S gas burns
At SO2Afterwards, using method washing similar with traditional pyrite-based sulfuric acid production technique, drying, catalyzed conversion, absorption.Wet contact method
It is then that sulfur dioxide is catalytically converted into sulfur trioxide in the presence of water vapor and directly condenses into acid without washing, drying.It is aobvious
And be clear to, wet contact method technique is more simple, is more advantageous to the recycling of system thermal.Due to most of H2S gas source all compares
It is relatively clean, so the application of wet contact method acid-making process is also relatively broad.It is generally believed that SO2+SO3Mass fraction is 0.3%-
Under conditions of 7%, wet process acid-making process is a kind of selection the most economic.Current most representative technology is Top, Denmark rope
The cryogenic condensation technique of the wet process sulfur process (Wet gas Sulphuric Acid, abridge WSA) of company, German Lucci corporation
With Kang Kaite (Concat) technique.
External WSA technology, which is to convert the various sulfide in sour gas to the concentrated sulfuric acid, the condensation dress of use
It is set to falling-film condenser.Technical process are as follows: sour gas burning generates SO2, it is converted to SO2Enter SO through cooling containing humid gas2Turn
Change device and generates SO3, SO3Enter condenser with the vapor of carrying and is directly condensed into acid.It is using sulfuric acid as final products, skill
Art is reliable, but complicated for operation, equipment rapid wear, invests also higher.
Cryogenic condensation technique is a kind of wet contact method acid-making process that Germany's Lucci corporation the 1930s proposes.The work
Condensation of sulfuric acid device is fountain packed tower in skill, is followed by demister.The technical process is: containing H2The sour gas of S is being burnt
It burns burning in furnace and generates SO2, SO2The catalyzed conversion in converter, the gas of converter is directly entered condensing tower out, sprays with tower top
The cold sulfuric acid counter current contacting of the circulation of leaching, is condensed into acid.The processing disadvantages are that use scope is limited, cannot handle volume after combustion point
Number SO2Gas lower than 3%, is only applicable to small-scale device.
Kang Kaite technique is also known as high temperature condensation process, is the wet of the improvement that Lucci corporation is released again after cryogenic condensation technique
Method contacts catalytic production sulfur process.High temperature condensation is SO3Gas and vapor condense into acid at high temperature.The condensation of the technique
Device selects Venturi tube condenser.The technical process is wet H2S gas and fuel gas cooperate, and burn in incinerator
Generate SO2, SO2It is aoxidized in converter, the gas after oxidation enters condensation Venturi tube, the hot sulfuric acid with high degree of dispersion
Parallel flow contact, generates sulfuric acid, and precipitating heat release finally carries out the cooling of gas and the separation of sulfuric acid droplet.The technique is particularly suitable
In treatment temperature height, H2S, CS2And CO2The low gas of content, can handle SO in combustion gas2Gas of the volume fraction down to 1% is simultaneously
Keep autothermal equilibrium.The method is also applied for the tail gas of processing Clausius equlity technique, and sulfur recovery rate is up to 99.5%.Product
The mass fraction of sulfuric acid can reach 93%.Compared with discharging desulfurization technique with Crouse, the investment of Kang Kaite technique is relatively low,
About there was only the 30% of Cross unit investment.In addition, Kang Kaite technique in addition to blower and circulating pump need electric power, does not need to add it
His energy.But the technique is only suitable for handling H2S, CS2And CO2The low gas of content, heat recovery rate is low, and product acid concentration is slightly lower.
The generally existing SO of existing three kinds of wet process acid-making process3When being condensed into sulfuric acid, it is solidifying to need to be arranged combusting silicone oil manufacture
The purpose of operation of tuberculosis, the operation is to create the nuclei of condensation, and enhancing sulfuric acid vapor condensation reduces sulfuric acid aerosol concentration in tail gas.
But in practical operation, it is limited to understanding and self-ability of the operator to technique, silicone oil combustion intensity is difficult to control, is difficult to fire
The nuclei of condensation for generating suitable concentration are burnt, causes the nuclei of condensation on the high side or on the low side, can not all be correctly obtained the effect of condensation of sulfuric acid in this way.
As country is to the pay attention to day by day in terms of environmental protection, and the exhaust emission standard being increasingly stringenter, so that compeling to be essential
Wanting a kind of can handle that high concentration and the hydrogen sulfide sour gas of low concentration, cost of investment are low, easy to operate, exhaust emissions is up to standard simultaneously
Sulfur recovery technology.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome operation existing for wet process acid-making process in the prior art multiple
Miscellaneous, equipment rapid wear, investment is high, and can not handle the defect of the hydrogen sulfide sour gas of high concentration and low concentration simultaneously, and provides
The multi-stage oxidizing sulphuric acid plant and acid-making process of a kind of hydrogen sulfide sour gas.Technique provided by the invention can handle highly concentrated simultaneously
The hydrogen sulfide sour gas of degree and low concentration, and significantly reduce plant investment and operating cost.
The present invention provides a kind of multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas, the multi-stage oxidizing sulphuric acid plant packet
Include a H2S burner, one and the H2S burner connected combination type reactor, a sulfuric acid vapor condenser and an acid mist
Trap；
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 cooling medium that circulates, the glass tube is located between the two sidewalls of the shell, the glass
One end that pipe is located at the cooling medium upstream is head end, and one end positioned at the cooling medium downstream is tail end, in the cooling medium
Upstream and downstream between the adjacent glass tube be connected to end to form the cooling medium of at least one one-way guide flow
Runner；
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.
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 low concentration (4%-15%mol) H2Stablize reaction under S operating condition.Burner load
Adjustment 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.
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 cooling medium channel of the one-way guide flow formed by glass tube can
It is 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 condenser.
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.With no restrictions to the shape for being formed by cooling medium runner at this, can be " bow "
Font, " Z " font or other shapes.
In the sulfuric acid vapor condenser, when cooling medium be air when, for cooperation cold air decline characteristic, under enterprising
Flow direction design out can be further improved the mobility of cooling medium, improves velocity of medium, then improves condensation efficiency.
In the present invention, preferably, the liquid outlet of the acid mist eliminator is also connect with the sulfuric acid blending tank.
In the present invention, preferably, the offgas outlet of the acid mist eliminator is also connect with a tail gas washing tower, washed in tail gas
Wash the SO of trace in tower2Pass through H2O2The washing of weak solution, by H2O2Direct oxidation is SO3, form sulfuric acid droplets, final tail gas
Qualified discharge.
The present invention also provides a kind of multi-stage oxidizing acid-making process of hydrogen sulfide sour gas, use multistage as described above
Producing acid by oxidation device carries out comprising following steps: first by H2The burning of S sour gas generates SO2Process gas, then by SO2Process gas is urged
Change oxidation and generates SO3Then process gas is condensed into sulfuric acid；H2H in S sour gas2The concentration of S is >=0.5%mol, described to rub
Your concentration is H2The mole of S accounts for H2The percentage of the mole of S sour gas.
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 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+n CO2+ 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, which depends on H in sour gas2S concentration,
The split ratio with air quantity and hot-air of burning.
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.From
The process gas temperature of the skill that goes into operation Gas Cooler is higher than dew-point temperature, to prevent the sulfuric acid vapor condensation deposition in downstream process from causing
Equipment corrosion, while being conducive to protect downstream sulfuric acid vapor condenser inner coating, while protecting quartz glass heat exchanger tube, reduction pair
The thermal shock strength of coating material and quartz glass heat exchanger tube.
In the sulfuric acid vapor condenser, the cooling medium is generally cold air.
In the present invention, preferably, being also passed through H in condensation process2O2Solution is used for SO3The trace carried secretly in process gas
SO2It is oxidized to SO3, then through condensation form sulfuric acid droplets.H is arranged in tail gas2O2Potent oxidation unit, the i.e. SO of trace2Pass through
H2O2The washing of weak solution, by H2O2Direct oxidation is SO3, sulfuric acid droplets are formed, and then collect by acid mist eliminator, it is so real
The minimum discharge of existing tail gas, tail gas SO2Can≤50mg/Nm3, realize minimum discharge, zero-emission of the current industry to environmental protection can be met
Technology expectation.
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).
In a better embodiment of the invention, the hot-air of sulfuric acid vapor condenser is sent out, is partially mentioned through secondary air fan
High pressure is sent to the combustion furnace of device leading portion as combustion air, and remaining air send chimney to be vented, to improve emptying end gas
Temperature and lift.
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 multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas provided by the invention and
Acid-making process, wherein after single-stage combustion, H2H in S sour gas2S total conversion is up to 99.9% or more；In catalytic oxidation process,
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 is dense
Degree can reach 97-98wt%, and free from foreign meter, 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.
Detailed description of the invention
Fig. 1 is the process flow chart of the multi-stage oxidizing sulphuric acid plant of the embodiment of the present invention 1.
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
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 multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas provided in this embodiment is as shown in Figure 1, the multi-stage oxidizing system
Sour device include a combustion furnace 4, one be connected with combustion furnace 4 combination type reactor 5, a sulfuric acid vapor condenser 1 is (such as Fig. 2 institute
Show) and an acid mist eliminator 6.
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 efficiency
It 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.
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；The adapter tube that first sect heat-exchanger 502, the second sect heat-exchanger 504 are connected with shell
There should be 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.Into
The lower section of port 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 semicircle
Shape structure, leakage fluid dram 13 are located at the bottom of semicircular structure.Certainly, housing bottom can for other along liquid discharge direction by
Tapered small 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 equipped with
One 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.In the upstream of the flow direction of the cold air as cooling medium
Two adjacent glass tubes between downstream, i.e. successively first (end) tail (end) is connected for upper and lower two adjacent glass tubes in Fig. 2,
To formed one from top to bottom, the cooling medium runner of one-way guide flow.In the present embodiment, two adjacent glass tubes pass through a U
Type band tubing 23 is connected to.
The cooling medium runner includes that a cooling medium inlet for being located at upper part of the housing and one are located at the cooling of lower part of the housing
Media outlet, cold air enter from cooling medium inlet, flow to cooling medium outlet along cooling medium runner and are discharged.This
In embodiment, which is the head end of glass tube 21, and cooling medium outlet is the tail end of glass tube 22.
In sulfuric acid vapor condenser 1 described in the present embodiment, by the cooling medium channel for the one-way guide flow that glass tube is formed
It is resistant to high temperature and deep-etching, avoids occurrence of equipment deformation and corrosion damage phenomenon in high temperature and severe corrosive environment, really
It has protected condenser to use for a long time, has improved 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.At a high speed
Fiber mist eliminator is woven to layered filter using the filter screen of high-intensitive fibre cleavages silk package PTFE, when containing sulfuric acid
When the process gas of drop (acid mist) passes through the filter, intercepted by forcing, the sulfuric acid gas that realization is carried secretly to acid mist and wherein is molten
The efficient trapping of glue, 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).
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 cooling medium runner at this, can be " bow " font, " Z "
Font or other shapes.
Wherein, cooling medium is generally cold air.When cooling medium be air when, for cooperation cold air decline characteristic,
The flow direction design of upper entering and lower leaving can be further improved the mobility of cooling medium, improves velocity of medium, then improves condensation efficiency.
In the present embodiment, the liquid outlet of acid mist eliminator 6 is also connect with sulfuric acid blending tank 7.
Correspondingly, the acid-making process in the present embodiment includes the following steps:
(1) sour gas burns
Combustion furnace 4 uses secondary firing, i.e., swirl flow device is arranged in burner hearth, is equivalent to the secondary Forced Mixing of setting,
Combustion intensity can be greatly improved.
(2) process gas catalysis oxidation
Process gas after burning makes SO using multi-stage oxidizing2Process gas catalysis oxidation generates SO3。
(3) sulfuric acid vapor condenses
The cooling medium channel of the one-way guide flow formed by glass tube is resistant to high temperature and deep-etching, avoid in high temperature and
Occurrence of equipment deformation and corrosion damage phenomenon in severe corrosive environment, it is ensured that 1 long-time of sulfuric acid vapor condenser uses, and improves
The safety in utilization and fluency of sulfuric acid vapor condenser 1.
(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 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: 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
The process flow chart of the multi-stage oxidizing sulphuric acid plant of the present embodiment, sulfuric acid vapor condenser as shown in Fig. 1~2, this
In embodiment, with flow 34328Nm3/ h, H2S concentration: 1%mol is acid gas, can produce sulfuric acid (93wt%) equivalent 142
Ton/day, 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 is firing
Burn the reaction time 1.5s in 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 multi-stage oxidizing sulphuric acid plant of hydrogen sulfide sour gas, which is characterized in that the multi-stage oxidizing sulphuric acid plant includes
One H2S burner, one and the H2S burner connected combination type reactor, a sulfuric acid vapor condenser and an acid mist are caught
Storage；
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 cooling medium that circulates, the glass tube are located between the two sidewalls of the shell, the glass tube position
It is head end in one end of the cooling medium upstream, one end positioned at the cooling medium downstream is tail end, in the upper of the cooling medium
The adjacent glass tube is connected to end to form the cooling medium runner of at least one one-way guide flow between trip and downstream；
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.
2. multi-stage oxidizing sulphuric acid plant 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. multi-stage oxidizing sulphuric acid plant 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. multi-stage oxidizing sulphuric acid plant as described in claim 1, which is characterized in that the inside of the combination type reactor is equipped with
3 catalyst beds and 2 sect heat-exchangers, the sect heat-exchanger be sequentially distributed in the two neighboring catalyst bed it
Between, be denoted as from top to bottom the first catalyst bed, the first sect heat-exchanger, the second catalyst bed, the second sect heat-exchanger and
Third catalyst bed；The bottom of the combination type reactor is additionally provided with a technique Gas Cooler.
5. multi-stage oxidizing sulphuric acid plant 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；Cooling Jie
Mass flow road is equipped with a cooling medium inlet and a cooling medium exports, and the cooling medium inlet is condensed close to the sulfuric acid vapor
The top of device, the cooling medium are exported close to the bottom of the sulfuric acid vapor condenser；
The acid mist eliminator is a high-speed fibre demister；The liquid outlet of the acid mist eliminator is also mixed with the sulfuric acid
Tank connection；The offgas outlet of the acid mist eliminator is also connect with a tail gas washing tower.
6. a kind of multi-stage oxidizing acid-making process of hydrogen sulfide sour gas, which is characterized in that it is used as Claims 1 to 5 is any
Multi-stage oxidizing sulphuric acid plant described in one 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 is condensed into sulfuric acid；H2H in S sour gas2The concentration of S >=
0.5%mol, the molar concentration are H2The mole of S accounts for H2The percentage of the mole of S sour gas.
7. multi-stage oxidizing acid-making process as claimed in claim 6, which is characterized in that H2H in S sour gas2The concentration of S is 1%
Mol or more, preferably 4%-15%mol.
8. multi-stage oxidizing acid-making process as claimed in claim 6, which is characterized in that H2H in S sour gas2The concentration of S is 20-
30%mol, preferably 29.16%mol.
9. multi-stage oxidizing acid-making process as claimed in claim 6, which is characterized in that H2The ignition temperature of S sour gas be 800~
1200℃；H2In the combustion process of S sour gas, 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；
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. multi-stage oxidizing acid-making process as claimed in claim 6, which is characterized in that when the inside of the combination type reactor
Equipped with 3 catalyst beds and 2 sect heat-exchangers, the sect heat-exchanger is sequentially distributed in the two neighboring catalyst bed
When between layer, the SO of first catalyst bed2Process gas inlet temperature is controlled at 380 DEG C or more；Second catalyst
The process gas inlet temperature of bed is controlled at 410 DEG C or less；The process gas inlet temperature control of the third catalyst bed exists
390 DEG C or less；
In the sulfuric acid vapor condenser, the cooling medium is cold air；H is also passed through in condensation process2O2Solution is used
In by SO3The SO for the trace carried secretly in process gas2It is oxidized to SO3, then through condensation form sulfuric acid droplets；SO3Water content in process gas
It is 9.96%；SO3Process gas enter the sulfuric acid vapor condenser inlet temperature be 285~295 DEG C, preferably 290~
295℃。
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| PCT/CN2019/128208 WO2020140799A1 (en) | 2019-01-04 | 2019-12-25 | Acid production device and acid production process using multi-stage oxidation of hydrogen sulfide acidic gas |
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| WO2020140799A1 (en) * | 2019-01-04 | 2020-07-09 | 科洋环境工程（上海）有限公司 | Acid production device and acid production process using multi-stage oxidation of hydrogen sulfide acidic gas |
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| 鞍钢钢铁研究所技术情报研究室主编: "《均热炉及初轧机译文集》", 鞍钢钢铁研究所出版, pages: 51 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020140799A1 (en) * | 2019-01-04 | 2020-07-09 | 科洋环境工程（上海）有限公司 | Acid production device and acid production process using multi-stage oxidation of hydrogen sulfide acidic gas |
| CN110127629A (en) * | 2019-04-25 | 2019-08-16 | 南京聚拓化工科技有限公司 | A kind of wet process sulfide prepares the device and technique of sulfuric acid |
| CN110127629B (en) * | 2019-04-25 | 2020-11-17 | 南京聚拓化工科技有限公司 | Device and process for preparing sulfuric acid from sulfide by wet process |
| CN110925782A (en) * | 2019-12-12 | 2020-03-27 | 伊犁新天煤化工有限责任公司 | Chemical acid gas treatment system and method |
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